MICROBIAL TRANSFORMATIONS
OF STEROIDS
ACADEMIC PRESS New York and London
A Handbook
William Charney Manager, Industrial Microbiology, Schering Corporation, Union, New Jersey
and
Hershel L. Herzog Director of Chemical Development, Schering Corporation, Bloomfield, New Jersey
1967
<3
COPYRIGHT © 1967, BY ACADEMIC PRESS INC.
ALL RIGHTS RESERVED
NO PART OF THIS BOOK MAY BE REPRODUCED IN ANY FORM, BY
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United Kingdom Edition published by ACADEMIC PRESS INC. (LONDON) LTD. Berkeley Square House, London W.l
LIBRARY OF CONGRESS CATALOG CARD N U M B E R : 68-18661
PRINTED IN THE UNITED STATES OF AMERICA
To Mita and Levonna
PREFACE
The principal purpose of this volume is to provide those who wish to use micro-bial transformations of steroids with a single source book for the period from 1937 to the present. This handbook should answer the following questions: Has a particular compound been prepared with the aid of microorganisms? If so, how efficient are these methods, and which among them is likely to be the best? Has a particular microbial genus (or species) been used with a particular substrate (or substrates), and what was the observed result? Where can the required culture be obtained? Is there a United States Patent or a published scientific article (through December 31, 1963, with selected entries thereafter) which discloses the product of the organism in question in a detailed example ?
The literature of this field has been spread widely in chemical and biological journals throughout the world. To the extent that we have been able, we have combed this literature and tabulated selected data which we believe may be useful. We have continued our scrutiny to the present, and all important developments subsequent to December, 1963, are discussed, with references appropriately noted in the Biblio-graphical Appendix. The Tables contain essentially no reference to this later work.
A secondary purpose of ours has been to survey the historical development and present status of the field. We have been closely associated with the commercial production of steroids for 15 years and have participated in some of the events which influenced the evolution of microbial transformations. It has been our intention to interpret the many developments in the theory and practice of the field from our largely applied viewpoint.
To the extent that we have considered theory, we have concentrated on the pro-cesses occurring within the steroid and have given little attention to the nature of the enzymes responsible for the observed changes or to the chemical changes which they might experience.
We extend our special thanks to the management of the Schering Corporation and to our colleague and guide, Dr. E. B. Hershberg, for their aid and understanding during the lengthy preparation of this volume. We also thank Miss Lisette Harris, Mrs. Marie Marshall, and Mrs. Elizabeth Wesson for their cheerful completion of the arduous task of typing the manuscript, and Miss Dorothy Mizoguchi for the trans-lation of articles published in Japanese.
We are grateful to Dr. C. H. Robinson and Dr. A. L. Nussbaum for reading and criticizing the historical and chemical transformation sections.
William Charney Hershel L. Herzog
October, 1967
vii
CHAPTER I
Introduction
Microbial transformations of organic compounds have been known in an empiri-cal way from the dawn of history. In almost every civilization, primitive or advanced, man has practiced the fermentation of fruit, grain, or milk to obtain intoxicating and nourishing dietary factors. Evidence of wine production from as early as approxi-mately 3000 B . C . has been found in excavations at Lachish and other sites. *
The rational application of these early techniques could come only after the scientific practice of organic chemistry and microbiology was begun. A sufficient understanding had developed by 1857 to provide the necessary background for the work of Louis Pasteur on the fermentation of sugar to lactic acid and ethanol. Herein was elucidated for the first time the concept that individual microbial species were re-sponsible for discrete chemical alterations of selected substrates.2"5 These experi-ments and their publication have been called "the birth of microbiology."5
EARLIEST WORK - NONSTEROID
After Pasteur and until the end of the 19th century, few studies of the application of microorganisms to organic chemistry were carried out. None of these were of an intensive, systematic nature, which might have emphasized the broader possibilities of a fusion of the two sciences,6?7 although Brown recognized that such possibilities did exist. He gave individual examples of the oxidation of secondary alcohols to ke-tones and of primary alcohols to aldehydes and carboxylic acids.
Beginning in 1896, Bertrand carried out extensive studies of the simple, oxida-tive process resulting from the action of Acetohacter xylinum on a series of polyhydric alcohols, and thereby established the generality of the illustrated scheme.8"10
1Wooley, L . , "The Beginnings of Civilization," Vol. I, Part II, p. 234. The New American Library, New York, 1965.
2Pasteur , L . , Compt. Rend. 45, 913 (1857). 3Pasteur , L . , Ann. Chim. Phys. [1] 58, 323 (1860). 4Pasteur , L. , Ann. Sei. Nat. 16, 5 (1861). 5Vallery-Radot, L. P . , "Pasteur Fermentation Centennial," p. 4. Chas. Pfizer and Co.,
Inc. , New York, 1957. 6Boutroux, L . , Compt. Rend. 86, 605 (1878). 7Brown, A. J . , J . Chem. Soc.,pp. 172 and 432 (1886). 8Bertrand, G., Compt. Rend. 122, 900 (1896); 126, 984 (1898). 9Bertrand, G., Ann. Chim. Phys. [7] £, 3 (1904).
10Bertrand, G., Bull. Soc. Chim. France 15, 627 (1896); 19, 502 (1898).
1
2 I. INTRODUCTION
CH?-OH CH20H I 2 I 2
H-Ç-OH Axylinum^ Ç=0 (H-Ç-OH)^ * " ( Η - 0 - Ο Η ) Λ
CH2OH CH20H
As "Bertrand's rule" was finally elaborated, it was shown that a pair of adjacent, eis, secondary hydroxyl groups, next to a primary hydroxyl group, suffice to establish conditions favorable for the oxidation.11 The reaction eventually became important for the conversion of sorbitol to Z-sorbose,12 an intermediate in the manufacture of vita-min C. Dihydroxyacetone, which has been used extensively in recent times to tan human skin in vivo (for cosmetic reasons), can also be made on a commercial scale in the same way.13 A favored organism for these reactions is Acetobacter suboxydans.
Following the work of Bertrand, the next major development in the field arose from the finding of Lintner and von Liebig14 that a fermenting yeast reduced furfur-aldehyde to the alcohol. Neuberg and his school explored the application of yeasts to a wide variety of substrates. Their studies are summarized in extenso by Fischer (F-245) and Stodola.15
EARLIEST WORK - STEROID
Steroidal substrates were used first, in 1937, by Mamoli and Vercellone (M-550, M-551), who began by extending the findings of the Neuberg school. They showed that fermenting yeast may be used to reduce 17-ketosteroids to 17ß-hydroxysteroids. This method had some passing importance in the manufacture of the male hormone,
fermenting yeast
testosterone (M-543), and later of the female hormone, estradiol (W-1085), but was superseded by more convenient and efficient nonenzymatic procedures.
Through the use of impure yeast cultures, Mamoli and Vercellone (M-538, M-540, M-542, M-552) discovered a useful class of sequential oxidation-isomeriza-tion reactions which they later attributed correctly to the action of the bacterial con-taminants (M-553). A representative transformation of this type (including a hydroly-sis step, as well) is the conversion of 3)3,21 -dihydroxy-5-pregnen-20-one 21-acetate to deoxycorticosterone by Corynebacterium mediolanum (Corynebacterium helvolum) (M-541, M-546). Schering (USA) employed a similar process to manufacture Reich-stein's Compound S (17α, 21-dihydroxy-4-pregnene-3, 20-dione) for a time. It is now clear that nonenzymatic methods are more efficient for the synthesis of Compound S.
11 Some later modifications of the rule are summarized by Sowden, J . S. , in "The Carbohydrates" (W. Pigman, ed.) , Po 132. Academic Press , New York, 1957.
12Wells, P. A., Stubbs, J . J . , Lockwood, L. B . , and Roe, E. T . , Ind. Eng. Chem. 29, 1385 (1937).
13Underkofler, L. A. , and Fulmer, E. I . , J . Am. Chem. Soc. 59, 301 (1937). 14 Lintner, C. J. , and von Liebig, H. J . , Z. Physiol. Chem. 72, 449 (1911). 15Stodola, F. H. , "Chemical Transformations by Microorganisms," Chapter 2. Wiley,
New York, 1958.
* •h
EARLIEST WORK - STEROIDS 3
c=o
CHLOH I 2
c=o
Mamoli and his colleagues also recognized a class of bacterial reductions, which they attributed to an anaerobic bacterial species identified as Bacillus putrificus. Al-
B. putrificus
though this culture has since been lost, the same (5/3) and related (5a) reductions have been demonstrated with a variety of aerobic and anaerobic microbial species and have some academic interest since they parallel normal modes of mammalian metabolism of 3-keto-Δ4-steroids.
Considered in the historical context, the timing of Mamoli's pioneering application of microbial methods to the organic chemistry of steroids was logical. Just a few years earlier the correct structure of the steroid nucleus had been established. In 1935 testosterone was isolated from steer testis by Laqueur and was shown to be a powerful male hormone in a variety of animal tests . The structure was established by Butenandt and Ruzicka during the same year. The possibility of important medical
Testosterone
application was on the horizon. We appreciate the element of inevitability in the de-velopment of microbiological transformations in the steroid field, arising as it did from the knowledge of the chemistry of yeasts developed by Neuberg and from the availability of 17-ketosteroid intermediates.
The period from 1940-1949, following the early efforts of the Mamoli school, was rather quiet with respect to the further evolution of microbial transformations. Eco-nomic incentive for further study was absent because adequate nonenzymatic method-ology had been devised for the synthesis of testosterone and related male hormone products, and estradiol. Also, the war disrupted scientific activity in Italy and Germany, where all the work had been done. Nevertheless, key observations which foreshadowed the subsequent explosive growth of the field were made.
Horvath and Kramli (H-406) in 1947 reported the 7-dehydrogenation of cholesterol with Azotobacter sp. and in 1948 (K-474, K-475) they reported the 7-hydroxylation of cholesterol with Proactinomyces sp. These reactions, both novel at this time, were the first examples of what later proved to be the most important contributions of
4 I. INTRODUCTION
microbiology to steroid chemistry. There was no basis, at the time these observa-tions were made, to appreciate their future import.
Turfitt (T-1029, T-1030, T-1031, T-1032, T-1034) studied the use of steroids, as a sole source of carbon for microbial growth, and the steroid transformation pro-ducts produced thereby. The key observations he made, which lay fallow until greater understanding of the field developed [cf. the work of Whitmarsh (W-l l l l ) and parti-cularly of Sih and his collaborators (Ap-79, Ap-83, Ap-95) ] were that cholestenone and 3-keto-4-cholenic acid were transformed by Proactinomyces erythropolis, albeit to a very minor degree, into 3-keto-4-androstene-17/3-carboxylic acid. The idea which this illustrated was that cholesterol conceivably might be transformed by a microbiological degradative method into useful steroid entities of substantially lower molecular weight.16
SIGNIFICANCE OF DISCOVERY OF ANTIINFLAMMATORY ACTION OF CORTISONE
The most important chapter in the history of microbial transformations of steroids has had to do with the synthesis of the hormones of the adrenal gland and of their more powerful and therapeutic ally selective synthetic analogs. Studies of the composition of steroids in bovine and other mammalian adrenal glands by Kendall, Reichstein, and Wintersteiner, and their respective collaborators, begun in the early 1930's, led eventually to the isolation, characterization, and structural proof of cortisone (1938).
CH20H I 2
c=o
Cortisone
Understanding of the therapeutic possibilities of this agent did not begin to develop until 1949, when Hench and associates17 announced the successful use of cortisone 21-acetate as a palliative in rheumatoid arthrit is . For their contributions to this discovery Hench, Kendall, and Reichstein shared the Nobel Prize.
Since rheumatoid arthritis was (and is) a grave and crippling disease, with a high incidence, there was a tremendous incentive to provide cortisone by an efficient syn-thetic technique. Sarett, among others, had been working on the partial synthesis of adrenocorticoid hormones, and in 1946 he achieved the first synthesis of cortisone. The cortisone for the Hench-Kendall clinical experiment was prepared at Merck based on synthetic methods devised by Sarett and by Kendall and his co-workers. The starting material was deoxycholic acid, which was readily available from bovine
16 At this time cholesterol was still the major starting material for steroid hormone synthesis. It was transformed by oxidation with chromic acid into dehydroepiandrosterone in about 10% yield. In the late 1940 Ts cholesterol was supplanted by diosgenin as the pre -ferred starting material.
17 Hench, P. S., Kendall, E. C. , Slocumb, C. H. , and Polley, H. F . , A. M. A. Arch. Internal Med. 85, 545 (1950).
ANTIINFLAMMATORY ACTION OF CORTISONE 5
bile. The introduction of the 11-oxygen atom, an essential element of structure, was a major task.18
While Merck, beginning in 1949, and Schering, in 1951, manufactured cortisone from deoxycholic acid, Peterson and Murray, biochemist and microbiologist, respec-tively, with the Upjohn Company, chose to attack the problem of the introduction of 11-oxygen by the potentially more direct, microbiological method. They have said (P-723) that they were stimulated to enter this field by the successes of the Mamoli school. They were also encouraged, early in their work, by the report of Hechter and collaborators19 that perfusion of deoxycorticosterone through isolated adrenal glands resulted in the formation of corticosterone by enzymatic 11/3-hydroxylation.
FIRST HYDROXYLATIONS
In 1950 Peterson and Murray observed the first microbial 11-hydroxylation, namely, the lla-hydroxylation of progesterone with the fungus, Rhizopus arrhizus. "The culture was isolated from the air when an agar plate was exposed on a window sill" (P-721). Shortly thereafter, Rhizopus nigricans was found to lla-hydroxylate progesterone in high yield. The first publication of this work in extenso was in a U. S.
c=o
patent which was issued in July 1952 (M-601) and described, with a wealth of detail, the hydroxylations at 60 and 11a of a variety of substrates by fungi of the order Mucorales. Selected examples of 7ξ- and 14 ξ-hydroxylations were also given.20
Emphasis was placed on lla-hydroxylation, since it was apparent that herein lay the great economic value of this invention.
The importance of the Murray-Peterson discovery was manyfold. It led to a new technology for the manufacture of adrenocortical hormones and, eventually, of their synthetic analogs. It introduced the use of fungi, heretofore unexplored as a source of enzymes for microbiological transformations. And perhaps most important of all, it caused a surge of interest in the field. Much new, basic information for science was developed subsequently from the study of microbiological transformation of steroids.
Colingsworth, Brunner, and Haines (C-134), also of the Upjohn Company, dis-covered the llß-hydroxylation of Compound S with the actinomycete, Streptomyces fradiae shortly after the original Murray-Peterson findings were made. This was to
18 Flow chart 26 from "Steroids" (L. F. Fieser and M. Fieser, p. 644, compounds I to DC. Reinhold, New York, 1959), is an accurate representation of the complexity of this process, as it was actually practiced on an industrial scale. More generally, the background for all important early developments in steroid chemistry is given in detail by the Fiesers.
19Hechter, O., Jacobsen, R. P . , Jeanloz, R., andSchenker, V., J. Am. Chem. Soc. 71, 3261 (1949).
20 Hydroxylation at the 8-position was also described, revised to 9OJ, and in some cases Iß.
Levy, H., Marshall, C. W., Pincus, G.
These assignments were later
Rhizopus nigricans
6 I. INTRODUCTION
be the prototype for a second class of hydroxylation of considerable commercial significance.
CH-0H
Compound S Hydrocortisone
The same investigators also found that Cunninghamella blakesleeana was consid-erably more efficient at promoting this same reaction (H-339).
The motives which induced Murray, Peterson, and their Upjohn colleagues to enter this field were equally impelling for Perlman, Titus, and Fried of Squibb. In-dependently,21 they discovered the 16a-hydroxylation of progesterone with an actino-mycete later shown to be Streptomyces argenteclus. In 1956, when the antiinflamma-tory activity of triamcinolone was reported by Bernstein (B-60), the considerable value of this hydroxylation was first appreciated (T-1002). Fried and his colleagues
Triamcinolone
also discovered the useful lla-hydroxylation of progesterone by Aspergillus niger early in their studies.
FIRST DEHYDROGENATIONS
An immediate and major result from all of these early findings was the improve-ment of the methodology of steroid chemistry and the opening of a new avenue for r e -search. Microbiological transformation studies were begun in the laboratories of most of the pharmaceutical houses with interests in steroid chemistry (Lederle, Merck, Pfizer, Schering, and Syntex, among others). Since Schering was producing cortisone acetate at this time and was attempting to develop a useful synthesis for hydrocortisone (cortisol), we were prompted to extend the investigations of the early workers into new lines which might improve our production techniques. In this connection we began, in 1953, the study of the enzymatic hydrolysis of hydrocortisone 11, 21-diacetate. The diacetate had been prepared 22 in the hope that a chemical hydrolysis might afford
21 The first Squibb patent application in this field was filed in July 1951. 2201iveto, E. P . , Gerold, C. , and Hershberg, E. B . , Arch. Biochem. Biophys. 43, 234
(1953).
FIRST DEHYDROGENATIONS 7
hydrocortisone. The 11-ester was then found to be exceptionally difficult to hydrolyze, and we turned to the use of microorganisms.
One of the early experiments, which was run by Nobile in our laboratories, was the treatment of the diacetate with Corynebacterium simplex. The rationale was that an apparently related and then unavailable culture, Corynebacterium mediolanum, had been shown by Mamoli to have a good esterase (M-541, M-546). As it turned out, C. simplex afforded an interesting new reaction product in high yield, but that product was not hydrocortisone. More detailed investigation with other substrates, particu-larly Compound S, showed that the major transformation was 1-dehydrogenation (H-389, N-671).
II 0CCH,
The microbial 1-dehydrogenation reaction was not new, having been described at a Gordon Conference in the summer of 1953 by Fried2 3 and published in November of the same year (F-284). Vischer and Wettstein had also observed 1-dehydrogenation (V-1056). In none of the cases described by Fried, Thoma, and KLingsberg or Vischer
ChLOH I 2
C=0
23 Josef Fried, not to be confused with his brother, John Fried, also a steroid chemist. All the early work in microbial transformations reported by J . Fried was done by Josef Fried.
8 I. INTRODUCTION
CH, i 3
and Wettstein, several of which are illustrated here, did a steroid with a pregnane skeleton pass through the dehydrogenation process to an identified product with side-chain intact. In all instances wherein a 1-dehydro product was characterized, either 1, 4-androstadiene-3, 17-dione, 17/3-hydroxy-l, 4-androstadien-3-one, or 1-dehydro-testololactone was formed, the side chain having been altered in the illustrated way.24
Since we had shown that C. simplex dehydrogenated without concomitant side-chain degradation, we were able to use this transformation to prepare the previously unknown 1-dehydro analogs of cortisone and hydrocortisone, later named prednisone and prednisolone, respectively. These were tested in animals by Tolksdorf, Perlman,
ÇHLOH CHLOH I 2 I 2
C=0 C=0
Prednisone Prednisolone
and their collaborators at Schering25 and found to be three to five times more potent than the parent 1, 2-dihydro compounds by a variety of criteria (H-387, H-389). In July 1954, prednisolone was given to M. M. Pechet, then at the National Institutes of Health, who with J . J . Bunim and A. Bollett tested the compound in an arthritic hu-man. This first test and the many subsequent tests with both prednisone and prednis-olone in corticoid-responsive diseases confirmed the enhanced potency predicted from the animal experiments. In addition, and even more important, they showed that there was essentially no drug-induced salt retention at therapeutic dose levels. Since salt retention had been a significant complication resulting from the use of cortisone and hydrocortisone, the improved therapeutic index of prednisone and prednisolone en-couraged a much wider use of adrenocorticoids in the treatment of dermatologie, allergic, and collagen diseases.
Using fermentation techniques, the Schering Corporation made prednisone and prednisolone broadly available early in 1955. These agents quickly supplanted corti-sone and hydrocortisone for most indications requiring systemic (as opposed to topical) treatment. These 1-dehydro compounds continue to be used widely (1966) in spite of the many additional synthetic corticoids which have been produced. In the
24 Vischer and Wettstein mentioned Chromatographie evidence for the formation of pro-ducts, from Compound S and cortisone, which had suffered no degradation.
25 Tolksdorf, S. , Battin, M. L. , Cassidy, J. W., McLeod, R. M., Warren, F. H. , and Perlman, P. L. , Proc. Soc. Exptl. Biol. Med. 92, 207 (1956).
F sol ani F. caucaslcum
FERST DEHYDROGENATIONS 9
subsequent development of the corticoid field, 1-dehydrogenation played a vital role. All synthetic corticoids for systemic use contain this structural unit.
The other contributions from microbiology toward the realization of new struc-tures have been in providing improved technology for manufacture. Triamcinolone, whose preparation and properties were announced by Bernstein and his collaborators
CH2OH
C=0
Triamcinolone
of Lederle in 1956 (B-60), was the first useful antiinflammatory agent to embody the potency-enhancing effort of the 9a-fluorine atom, discovered by Fried and Sabo in 1954. To counteract the concomitant, increased, s alt-retention component, also con-tributed by the halogen, the insertion of Δ1 -unsaturation was insufficient. Bernstein found that the presence of a 16a-hydroxyl group effectively blocked salt retention in 9a-fluorosteroids, at the expense of the potency enhancement normally found in 9a-fluorocorticoids. Triamcinolone has essentially the same milligram potency as pred-nisone and prednisolone, but has been found to be somewhat more active in the treat-ment of certain, rather common dermatologie conditions, particularly psoriasis. This property has led to its widespread use. The considerably poorer therapeutic index of triamcinolone (as measured in dogs) does not seem to have become a problem in human medicine, although the pattern of side effects varies somewhat from that usually observed with other synthetic corticoids.
Bernstein and his associates achieved the introduction of the lto-hydroxyl group by chemical means in their first synthesis, and hence microbiology cannot be said to have contributed significantly to this aspect of the discovery. In the ultimate commer-cial exploitation, however, advantage was taken of the findings of Perlman, Titus, and Fried (P-718), and subsequent improvements by Thoma and Fried (T-1002), to intro-duce the 16a-hydroxyl group microbiologically. Lederle eventually cross-licensed with Squibb, exchanging triamcinolone rights for rights to use the 9a-fluoro discovery of Fried and Sabo and the 16a-hydroxylation technology.
Many synthetic corticoids were introduced following the discovery of triamcino-lone. These include triamcinolone 16,17-acetonide, 6a-methylprednisolone, 16a-methyl-9a-fluoroprednisolone(dexamethasone), 16/3-methyl-9a-fluoroprednisolone (betamethasone), 6a-fluoro-16a-methylprednisolone (paramethasone), 16-methylene-prednisolone, and 6a, 9a-difluoro-16a-hydroxyprednisolone 16,17-acetonide (fluocino-lone acetonide). Microbiology played no essential role in their discovery, although in some cases microbiological technology has been employed to advantage in their manu-facture.
MANUFACTURE OF NATURAL AND SYNTHETIC CORTICOSTEROIDS
As far as we are able to determine, the present status of manufacture of the important bulk corticoids is illustrated in the flow diagrams which follow. Since manu-facturing details are rarely available for public inspection, there is an element of guesswork in some of these charts. Paramethasone and üuocinolone acetonide are thought to require microbial 11/3-hydroxylation steps in their manufacture.
10 I. INTRODUCTION
Hydrocortisone and Cortisone
Upjohn
Hydrocortisone
CH,OH
Cortisone
Schering A.G. and Pfizer
CHOH I 2
c=o
*- Cortisone
Compound S Hydrocortisone
Dexamethasone and betamethasone have been made principally from deoxycholic acid and hecogenin, respectively, by nonmicrobiological routes.
Microbiology has had a passing role in the discovery of the anabolic agent, 1-dehydromethyltestosterone. First prepared by Nobile in our laboratories by the ac-tion of Cornybacterium simplex on methyltestosterone (N-667a), and independently
Progesterone
MANUFACTURE OF CORTICOSTEROIDS 11
Upjohn
Prednisolone and Prednisone
Prednisolone
CH-OH
Schering A.G. Prednisone
CH,OH
> - Prednisone
Prednisolone
by Vischer, Meystre, and Wettstein (V-1052), its application to medicine was pioneered by Ciba. It is questionable whether the microbiological route to this compound has any current commercial importance.
I - Dehydromethyltestosterone
NEW TRENDS IN RESEARCH
The most interesting new prospect for the commercial application of microbio-logical transformations comes from the work of Sih and his collaborators. In the
12 I. INTRODUCTION
course of his studies on the microbiological degradation of steroids, Sih observed that estrone and estradiol were very resistant to attack by Nocardia restrictus, which he showed degraded nonaromatic steroids readily (e.g. , androstenedione) (Ap-83).26
Since N. restrictus was also capable of using cholesterol as a sole carbon source, Sih conceived that a suitable cholesterol-like substrate might be devised which would suffer side-chain degradation to a 17-ketosteroid, followed by A-ring aromatization, to afford estrone. From earlier studies by Dodson and Muir (D-170, S-849) of the aromatiza-tion of 19-hydroxy-4-androstene-3,17-dione, taken together with these new observa-tions, he concluded that 19-hydroxy-4-cholesten-3-one would be a suitable substrate for conversion to estrone. In the first tests reported, Sih and Wang (Ap-83) obtained
Estrone
N. restrictus Estrone
an 8% yield of estrone from the action of N. restrictus. Later improvements both in choice of substrate (19-hydroxycholesterol 3-acetate) and culture (CSD-10, an uniden-tified organism isolated from soil) have given estrone in 72% yield (Ap-81).
AcO'
Pb(0Ac)„
H0H2C
Estrone suitable
microorganism AcO'
Zn
AcO'
26 The work of Sih depended in great part on the earlier findings of Dodson and Muir (D-169, D-170, D-171, D-172), who established the fundamentals of microbial A-ring aromatization and B-ring cleavage of androstenedione and related structures.
NEW TRENDS IN RESEARCH 13
Since 19-hydroxycholesterol 3-acetate is readily available from cholesterol by the il-lustrated synthesis, it is possible to predict that this method or one closely allied to it will supplant presently used technology for estrone manufacture to some degree. Estrone, in addition to its uses as a female hormone is a key intermediate for the commercial synthesis of many widely used contraceptive agents. It has been selling for a price in the range of $0.50-$1.00/gram (1965).
In a broader sense, Sih and others have shown that a number of microbial genera, e .g. , Pseudomonas, Mycobacteriurn, Corynebacterium, Proactinomyces, etc., are also able to use cholesterol as a sole carbon source. It is reasonable to assume that re-presentative species of all these genera will be useful for estrone production in the same way thai No cardia restrictus has been (Ap-95). Sih has also shown that sub-strates related in structure to cholesterol, like ß-sitosterol, can act as sole carbon sources for Nocardia. By analogy with the cholesterol case, 19-hydroxy-4-stigmasten-3-one has been used to prepare estrone (Ap-83). The importance of this finding is that ß-sitosterol is a somewhat cheaper and more readily available raw material than cho-lesterol. It occurs widely in plants and has been accumulated for many years by the Upjohn Company as a by-product of stigmasterol purification. Upjohn has been purch-asing soybean sterols (from General Mills), from which they separate stigmasterol for use as a starting material in progesterone manufacture. The combined ß-sitosterol-campesterol by-product, which is produced in considerably larger amounts than the de-sired stigmasterol, has been cast in large blocks and buried in the ground for want of a better application. This sterol mine, which up to now has had essentially no value, may become the major source for estrone in the future.
'CVH-C;:C H- HP Ha H c:xtfCV?^<C
H2 C H^C H, H,
/3-Sistosterol Campesterol
This brief history has emphasized those discoveries which have had the greatest impact on commerce, because these findings were also pivotal in stimulating the sub-sequent studies of mechanism, and thereby had also the greatest impact on science. A more highly developed appreciation for the mechanistic basis of microbiological trans-formations was developed by Hayano, Talalay, Bloom, and Shull and their respective collaborators, and most recently by Ringold and Sih, all following the breakthrough dis-coveries and applications of the 1949-1954 period. Although this appreciation has until now had no decisive effect on the development of the field, which was shaped principally by the earlier, empirical findings, we may see in the work of Sih and his students the first instance of the successful synthesis of theory and practice.
In summary, microbiology applied to steroid chemistry has resulted in major contributions to technology, medicine, and science. Murray and Peterson, and Perlman and Fried laid the basis for the efficient application of microbiology to the synthesis of antiinflammatory steroids. The renewed interest in the field which they provoked led then to the one finding which was directly implicated in an improvement of therapy, namely, the application of microbial 1-dehydrogenation to the preparation of synthetic adrenocorticoid substances in our laboratory. Studies of mechanism which followed have clarified certain aspects of the stereochemistry and mechanism of microbial transformations and have established relationships with the larger corpus of knowledge of enzymatic chemistry.
CHAPTER II
CHEMICAL CLASSIFICATION OF MICROBIAL TRANSFORMATIONS OF STEROIDS
THE ROLE OF ENZYMES IN MICROBIAL TRANSFORMATIONS
Practical Implications Microbial transformations of steroids are part of the larger class of organic
chemical reactions which are catalyzed by enzymes. The microorganism functions as a convenient source of the required enzymes and, in some cases, provides iden-tifiable reagent species (cofactors) which act on the steroid in the presence of the enzyme or contribute to the regeneration of the active site on the enzyme. That the reactions are indeed enzymatic has been proved in several cases by the isolation of the crystalline enzyme from the microbial species and by the subsequent transforma-tion of the steroid in vitro, using the crystalline enzyme and an added reagent. The resulting transformation was identical with that obtained employing the intact micro-bial system with the same substrate.
Hiibener and collaborators have isolated a crystalline "20/3-hydroxy steroid de-hydrogenase" (H-410) from Streptomyces hydrogenans, which on incubation with a wide variety of 20-ketosteroids (S-803) afforded the corresponding 20/3-hydroxy com-pounds in high yields, but at rates which varied with the functional groups elsewhere in the molecule. The enzyme also catalyzed the oxidation of 2 Oß-hydroxy steroids back to 20-ketosteroids in the appropriate medium (H-410). NADH or another hydrogen source, e .g . , NADPH, is required for the reduction (H-408), the stoichiometry of which is illustrated. In the microbial culture the NADH (or NAD+) is regenerated by an appropriate reducing (or oxidizing) system already functioning to supply the other needs of the organism for the same coenzyme.
CH3 I 3
c=o
^ 3
HO-C-H
enzyme NADH 4- H 4- NAD
Another crystalline enzyme which has been studied is the isomerase of Kawahara, Wang, and Talalay (K-437, K-438), an induced enzyme isolated from Pseudomonas testosteroni. In this case, Malhotra and Ringold (Ap-44) have proved that the reaction
is entirely intramolecular and that no reagent or cof actor is required, of this reaction is discussed in the section on isomerization.
The mechanism
14
ROLE OF ENZYMES IN MICROBIAL TRANSFORMATIONS 15
An interesting example of an endogenous reagent class was described by Gale, and associates (G-291), who have shown that vitamin K2(35) can be isolated from Bacillus sphaericus. These investigators concluded on the basis of rate and inactiva-tion-reactivation studies with a cellfree Δ1 -dehydrogenating system derived from B. sphaericus that vitamin K ^ ^ is the natural cofactor for this reaction. Talalay27
prefers to view the role of vitamin K2(35) as that of a secondary hydrogen acceptor with a flavin acting as the primary oxidizing agent.
The regeneration of the oxidized forms of coenzymes or reagents of the NAD, flavin, or vitamin K types depends in the final analysis on oxygen from the air . For efficient transformation to take place, oxygen must be placed in intimate contact with the cellular material so that diffusion into the cells can occur. The solubility of oxy-gen in aqueous media is limited, which means that efficient aeration and agitation may be required to maintain an oxygen-saturated medium. Shake-flask agitation may be inadequate, which sometimes explains the observed superiority of the aerated, inter-nally agitated fer mentor in achieving the desired transformation.
As a practical matter, the microorganism of choice provides the necessary enzymes and cofactors for the desired transformation. It has never been necessary to do more than provide the organism with a medium which is both suitable for growth and known to provide adequate levels of enzymes and cofactors by direct test with the steroid substrate in question. The knowledge of the enzymatic nature of these reac-tions, however, does serve to instruct the user to seek optimum pH and temperature conditions, known to be important factors in controlling enzymatic reaction ra tes . These optima are not necessarily the same as the optima for enzyme production, and so, the phasing of steroid transformations as a function of the microbial growth cycle can be quite important. An illustration of this idea is the separation of the growth of the organism from the transformation of the steroid. This is accomplished by filtra-tion of the mycelium (S-871) [or spores (V-1048)] after growth under optimum condi-tions, followed by washing, and resuspension of the cellular material in a medium selected as optimum for transformation (often one in which there is no further micro-bial growth).
In some instances it has been proved that microorganisms produce enzymes for the transformation of steroids in response to a steroidal enzyme inducer contained in, or added to, the medium. Septomyxa affinis has been shown by Murray and Sebek (M-647) and Koepsell (K-456) to produce its 1-dehydrogenase best in the presence of 3-ketobisnor-4-cholen-22-al. This inducer did not, however, induce the enzyme(s) responsible for the Baey er -Villiger type reaction which S. affinis is also known to cause.
On the other hand, in the many cases in which microbial cultures are grown in steroidfree media, filtered to separate the mycelium [e.g. , Curvularia lunata (S-871)] or spores [e .g . , Aspergillus ochraceus (V-1048)], and the resulting, cellular material resuspended in water to which steroid is then added, no enzyme induction is likely to be involved. The transformation with these resting cells most probably results from
27Talalay, P . , Ann. Rev. Biochem34, 347 (1965).
16 II. CHEMICAL CLASSIFICATIONS
the action of enzyme synthesized during an earlier growth stage when exogenous ste-roid was absent.
To achieve optimum results with a given culture on a commercial level it is ob-viously desirable to know whether the required enzymes are induced or constitutive. In the laboratory it is judicious to avoid conclusions concerning a failure to transform until it is clear that this failure does not arise from inadequate conditions for enzyme induction.
Many organisms produce an overabundance of steroid-transforming enzymes, which lead, in turn, to multiple transformations, (e.g. , Rhizopus arrhizus hydroxyl-ates progesterone at both the 6/3- and 11a-positions). It is sometimes desirable to sup-press selectively the formation of the enzyme which leads to by-product formation or to inhibit the competing reactions after the enzymes have been formed. This has been accomplished in a few instances, but expectation for success in a previously untried case is modest at best. Dulaney, Stapley, and Hlavac (D-193) showed that the 6ß-hydroxylating enzyme of Aspergillus ochraceus requires zinc ion for its formation. Growth of cultures in zinc-deficient media effectively abolished the 6ß-hydroxylating ability of the culture without damaging its lla-hydroxylating power. Sih and Weisen-born (S-897) have described the partial inhibition with cyanide ion of the 1-dehydrogen-ation of progesterone by Nocardia restrictus. In this case the major steroidal pro-duct became 9a-hydroxyprogesterone. Sih attributed the diminished rate of 1-dehydro-genation to inhibition of a coenzymatic oxidation-reduction system by the cyanide (S-885).
As far as we know, transformations of steroids, carried out with intact micro-bial cells, occur within the cell and not in the medium surrounding the cell.28 To enter the cell the steroid being transformed must dissolve to some extent in the medium so that it can diffuse through the cell wall and into the enzyme-rich interior. The practical implication of this requirement is that solubility and rate of diffusion may become the rate-limiting factors for transformation. Most steroid substrates ordinarily employed have modest, though measurable, solubilities in water and in the aqueous media used for microbial culture. To ensure saturation of the medium and to minimize this rate-limiting effect, steroids are often introduced into reactions in micronized form or, more conveniently, in solution in a water-miscible solvent from which precipitation in very fine particles occurs upon dilution with the aqueous medium containing the microorganism.
The experimental findings summarized in this treatise may be interpreted rea-sonably to show that microbial enzymes are not highly substrate specific.29 The alter-nate explanation for the diversity of substrates which a given species can transform is that the organism has a different enzyme for each new substrate. The latter explana-tion is much less satisfying, and no evidence has been adduced in its support.
THE CLASSES OF CHEMICAL REACTIONS It is probably true that any class of enzyme-catalyzed reaction presently known,
or to be discovered, will eventually find an illustration in the microbial transformation of steroids. At the present time examples of all of the listed categories are known.
28An apparent exception is the report of Krider, Cordon, and Wall (K-478) that cultures of Aspergilli and Penicillia produce an induced, extracellular saponase in response to the pres-ence of saponins.
29Very recent transformations of steroids of 9j3,10a-configurâtion ("retrosteroids") illus-trate that there is no requirement for anything approaching a "natural" steroid structure. Cf. French Patents 1,372,850, 1,372,851, and 1,372,852 issued to N. V. Philips Co. of The Netherlands (see also Ap-16, Ap-92, Ap-93).
CLASSES OF CHEMICAL REACTIONS 17
1. Oxidation a. Hydroxylation b. Dehydrogenation c. Epoxidation d. Oxidation of alcohols to ketones or aldehydes e. Oxidation of ketones to esters or lactones f. Oxidation of sulfides to sulfoxides g. Oxidation of amines to ketones h. Oxidative degradation - a composite
2. Reduction a. Reduction of ketones, aldehydes, and acids to alcohols b . Reduction of double bonds c. Reduction of bromide
3. Esterification, amide formation, and hydrolysis a. Hydrolysis of esters to give steroid alcohols b . Esterification of steroid alcohols to esters c. Hydrolysis of oxides to alcohols d. Hydrolysis of acetals to steroid alcohols e. iV-Acylation of amines
4. Isomerization 5. Miscellaneous addition, rearrangement, and elimination processes 6. Resolution of d,l -mixtures In the application of these reactions to problems in organic chemistry, one must
recognize that each reaction class is likely to have substrate limitations. Superim-posed on these limitations are the normal difficulties associated with reproducing ex-perimental conditions in, and results derived from, biological systems. In the likely event of the absence of precisely applicable earlier findings, it is desirable to select an organism for the transformation being sought, which prior work has shown to be suitably nonspecific in substrate requirement. To help with these choices the tabular material presented in the later chapters has been provided.
The discussion of reaction classes with illustrations is offered here to give a concise overall view of the historical basis of the field, and its present condition, with particular reference to applications in organic chemistry and technology.
Oxidation The most important single category of microbiological transformations is oxida-
tion. The impetus for the recent, explosive development of the entire field came from the discovery of the fungal hydroxylation process by Murray and Peterson. At present, the only steroid transformations with continuing technological significance are hydroxy-lation and dehydrogenation, because of the ways in which they are used as parts of the syntheses of adrenocortical hormones and analogs. A promising new application, which remains to be proved on a commercial scale, is the oxidative degradation of sterols to estrone. This transformation may have great significance for the manu-facture of estrogens, progestins, and related contraceptive drugs. The many other transformations which are described here have special interest for the insights they provide into the biochemistry of microbial systems and for their applications to diffi-cult synthetic problems.
18 Π. CHEMICAL CLASSIFICATIONS
Hydro xylation
It is known that enzymatic hydroxylation processes for steroids observe these rules. (a)The entering oxygen atom is provided by gaseous oxygen (usually from the air), and not by water or any other oxygen-containing compound present in the medium prior to the initiation of the aeration process, (b) The stereochemistry of the carbon atom which is hydroxylated is always preserved. The newly formed hydroxyl group has the same configuration as had the hydrogen atom which occupied the same site prior to reaction. Thus, 1 la-hydrogen is transformed into 11a?-hydroxyl, 11/3-hydrogen into 1 Iß-hydroxyl, etc.
The evidence for the first rule comes from the work of Hayano, Dorfman, and associates. In the earliest studies they showed that beef adrenal homogenates could be used to llß-hydroxylate a variety of steroids which were saturated at C- l l (H-372). When labeled oxygen and ordinary water were used in the incubation system, the label was incorporated in the resulting 11-oxygenated steroid. When oxygen-labeled water and ordinary oxygen were used, no label was introduced in the resulting 11-oxygenated product. It was also proved that Δ9 ( 1 1 ) -steroids are not precursors of llß-hydroxy-lated steroids produced using beef adrenal homogenates as the enzyme source.30
Hayano, Dorfman, and collaborators showed later that the conclusions about the source of incorporated oxygen were equally true for microbial hydroxylations at 6/3, 11a, l lß , 12β, 15α, 17α, and 21 (Η-374, Κ-485).
Hayano, Peterson, and collaborators (H-371) and Corey, Gregoriou, and Peter-son (C-137) demonstrated that stereochemistry is preserved at the carbon atom which undergoes substitution. The former carried out the 11a-hydroxylation of pregnane-3,20-dione-lla,12a-H3 with Rhizopus nigricans and showed that tritium was lost at the 11- but not at the 12-position. Complementary experiments by Corey, using l l ß -deuterated pregnane-3,20-dione and Rhizopus nigricans afforded lla-hydroxypregnane-3,20-dione-llß-H2 (label retained). This proved that deuterium on carbon which be-comes substituted will survive the oxygénation process if the deuterium configuration is not the same as that taken by the entering oxygen. Taken together, the cited studies provide the basis for rules (a) and (b), and no contradictory evidence has, as yet, been found.
Ringold31 has put forward the interesting proposition that hydroxylation at 2ß9 6ß, 10ß, and 17α, in systems capable of being enolized toward these positions, in-volves the enol as an activated species. Ringold then suggests that both the enoliza-tion process and oxygen introduction involve enzyme participation, the OH+ attacking
3 0Hayano, M. , and Dorfman, R. I. , J. Biol. Chem. 211, 227 (1954).
3 1 Hayano, M. , in "Oxygenases" (O. Hayaishi, e d . ) , pp. 225-229. Academic P r e s s , New York, 1962.
CLASSES OF CHEMICAL REACTIONS 19
reagent being generated by the action of enzyme on oxygen. It seems to us that it may only be necessary to assume that enzyme is responsible for generating the enol. At this point undissociated oxygen can react with the enol, as has already been shown by Barton32 for the nonenzymatic 17a-oxygénation of 20-ketopregnanes in the presence of strong base (ί-butoxide ion) and oxygen. If our proposal were indeed true, the first product of this type of microbial oxygénation would be hydroperoxide, as observed by Barton in the chemical process, and not the hydroxy compound. Completion of the reaction would then require the enzyme-mediated reduction of hydroperoxide to hy-droxyl (e.g. , by NADPH). Stable compounds bearing hydroperoxide at the 10/3- and 17o?-positions have been described by Shapiro, Legatt, and Oliveto33 and Barton,32
respectively. These intermediates might be used to establish whether hydroperoxides can be reduced by a hydroxylating culture.
The rather surprising paucity of microbially induced 2a-, to-, l t a - , and 17/3-hydroxylations is consistent with the thesis that the enzymes which lead to 2/3 -, 6β -, 10/3 -, and 17ûf-hydroxylations are concerned principally with the enolization process and that the oxygénation stage is controlled by purely chemical factors. It is well established, for example, that electrophilic chemical attack at the 6-position, under kinetic control, is directly entirely to 6/3, even though the thermodynamically more stable species is the to-substituted product.
We believe it might be instructive to attempt the independent confirmation of the enolization hypothesis according to either one of the following schemes.
If a 17a-20-ketopregnane (e.g. , 17a-deoxycorticosterone) is subjected to the ac-tion of a 17a-hydroxylating organism (e.g. , Trichothecium roseum) the isolation of either a 1 la-hydroxy-20-ketopregnene (e.g. , Compound S) or a 17ß-20*-ketopregnane (e.g., deoxycorticosterone) would give important evidence for the enolization hypothe-s is . Since the formation of the former would be an apparent violation of the rule for
Bailey, E. J. , Elks, J . , and Barton, D. H. R. , Proc. Chem. Soc , p. 214 (1960). 3Shapiro, E. L . , Legatt, T . , and Oliveto, E. P . , Tetrahedron Letters, p. 663 (1964).
20 II. CHEMICAL CLASSIFICATIONS
CH20H
C=0 C - 0 "
reketonization CH,0H I C=0
Botrytis peoniae
reketonization
reketonization
preservation of configuration in the hydroxylation process, it would be best explained by the prior enolization of the starting material, thereby destroying configuration at the 17-position. If the oxygénation process were incomplete, it might still be possible to detect deoxycorticosterone formed by the reketonization of the enol to the normal, more stable 17ß-form.
The second scheme involves the use of a 10a-3-keto-A4-estrene as the substrate for what is normally a 10/3-hydroxylation process. The reasoning follows the same line developed for the first scheme.
At those sites which cannot be activated by enolization, a mechanism for hydrox-ylation other than that proposed for 2/3, 6)3, 10/3, and 17a must be operating. Hayano has enumerated the sequence of steps as follows: (a) oxygen activation, (b) substrate activation, if any, and oxygen transfer, and (c) regeneration of coenzymes. She sug-gested that the Jrydroxylation enzyme acts by providing the species OH+ from oxygen, NADPH, and a proton. The resulting ion then displaces the hydrogen atom by OH, with retention of configuration, at the site in the steroid under attack.
While this hypothesis is interesting, it is not compelling. Since it is already well recognized that molecular oxygen can react with electron-rich centers or radicals without the intervention of an agent (e.g. , enzyme) whose purpose might be to activate oxygen, one may argue that the oxygénation process at a saturated carbon atom seems
CLASSES OF CHEMICAL REACTIONS 21
to require activation of the C - H link only. One might therefore postulate that the function of the oxygénation enzyme is to confer upon the C-H link either radical or ionic character.
C-H ^ C _ \ _ _ _ H
*- C* H+ (C+ H")
The dashed line symbolizes the bond which is incompletely broken, but polarized, as a result of enzyme action. Given one of these premises, one may then depict the oxygénation process in the illustrated terms below. The first product of such a reac-tion will be a hydroperoxide which then requires reduction with NADH or an equivalent
[e n z y m e
H i 0
i \ Vu
fil n z y m e 1
) Electron pair migration )
H / v 0 l <> l l
Single electron migration
reducing system.34 This scheme embodies the 1 : 1 molar relationship of oxygen to NADH which Cooper, Estabrook, and Rosenthal35 find exists for steroid hydroxyla-tions.
H I
R-C-0-O-H I
R'
+ NADH + H R-C-OH + I R'
NAD +
One merit of the hydroperoxide proposal is that it might be subject to experi-mental test. As has already been pointed out, reasonably stable 10j3- and 17a-hydro-peroxides have been prepared. One might prepare 17a-hydroperoxyprogesterone as a reference and carr ier substance to identify the hydroperoxy intermediate, if indeed one be formed, from the 17ai-hydroxylation of C14-labeled progesterone with a suitable microorganism [ e . g . , Cephalothecium roseum (H-374)]. Incubation of a
So Kaufman [in "Oxygénases" (O. Hayaishi, ed.) , p. 170. Academic Press , New York, 1962] has summarized four proposals for a general mechanism of oxygénation, of which one is the formation and reduction of an intermediate hydroperoxide depicted here. B. Imelik [Compt. Rend. 226, 2082 (1948)] reported that Pseudomonas aeruginosa caused the transient formation of cyclohexane hydroperoxide when cyclohexane was the substrate.
35Cooper, D. Y. , Estabrook, R. E . , and Rosenthal, O. , J . Biol. Chem. 238, 1320 (1963).
22 Π. CHEMICAL CLASSIFICATIONS
17a-hydroperoxy substrate with a 17o;-hydroxylating culture would help to decide whether 17a-hydroperoxyl can indeed be reduced to 17a-hydroxyl under these condi-tions .
Sites of Reaction, la-Hydroxylation. Dodson, Goldkamp, and Muir (D-162, D-163) observed ΐα-hydroxylation with[Pénicillium sp. on 4-androstene-3,17-dione, 5a-androstane-3,17-dione, and 3ß-hydroxy-5-androsten-17-one (dehydroepiandro-sterone). The organism also oxidizes the 3-hydroxyl and isomerizes the double bond,
but hydroxylation precedes these reactions. Few instances of la-hydroxylation are known. Some recent, interesting examples were given by Sax and associates (Ap-68). These are discussed in greater detail under 2a-hydroxylation.
1/3-Hydroxylation. Greenspan and Schaffner, in association with our laboratory, reported Iß-hydroxylation of Compound S with Rhizoctonia ferrugena (G-315). The configuration of the entering group was established by Nussbaum (N-688, N-689)
through comparison with the same product synthesized from ruscogenin (lß-hydroxy-diosgenin), a sapogenin from Ruscus aculeatus. The same transformation has been seen in the androstane series with Haplosporella and Xylaria sp. (D-165). Nozaki has demonstrated Iß-hydroxylation of digitoxigenin (N-679) and 3)3,140, 21-trihydroxy-5ß-pregnan-20-one (Ap-59) using Absidia orchidis. In these latter instances, the site of hydroxylation seems to be influenced by the configuration or nature of the substituent (s) at the 5- and/or 14-position, since Absidia hydroxylates principally at the 11a- and 1 Iß-positions in the 4-pregnene series (H-334, N-682, S-841).
2a-Hydroxylation. This transformation was recently seen for the first time by Sax and co-workers (Ap-68) and Modelli (Ap-51). The former reported that Nocardia corallina afforded simultaneous la- and 2a-hydroxylation of ethisterone (I), 9a-fluoro-llß,17ß-dihydroxy-17a-methyl-4-androsten-3-one (II) (together with oxidation at the 11-position), andllß,16a,17a,21-tetrahydroxy-4-pregnene-3,20-dione 16,17-acetonide. No monohydroxylated products were isolated. Since N. corallina is normally (and in these cases, also) a Δ1 -dehydrogenating organism, Sax has proposed that the Δ1 -compounds are intermediates in these hydroxylation processes. This was proved with the Δ1-containing compound (III), which was dihydroxylated under the same fermenta-tion condition as (II). A different mechanism from those normally operating in hydrox-ylations must be involved. Sax has suggested for consideration a number of pathways from the A1'4-dien-3-one to the la,2a-dihydroxy product. To his suggestions might also be added direct eis hydroxylation of the Δ1 double bond in the way that chemical
CLASSES OF CHEMICAL REACTIONS 23
CEECH
(I)
(II) (III) agents like permanganate do in related unsaturated systems. This question remains to be settled.
Modelli (Ap-51) has described the 2o?-hydroxylation of 19-nortestosterone (17j3-hydroxy-4-estren-3-one) and 19-nor-4-androstene-3,17-dione with Nocardia italica. These are the only examples of 2a-hydroxylation which arise from a "normal" mechanism of hydroxylation at a saturated carbon (as distinct from the Sax results).
..OH
• OH
Satisfactory, conventional chemical methods for introducing the 2a-hydroxyl group are available.
2/3-Hydroxylation. Simultaneous reports from our laboratories (G-315, H-383) and by Dodson, Goldkamp, and Muir (D-162, D-163) contained the first descriptions of 2ß-hydroxylation. We found that Streptomyces sp. and Rhizoctonia ferrugena trans-formed Compound S. The Searle workers used 4-androstene-3,17-dione as the
CH20H
:0H
j Streptomyces sp.
Rhizoctonia ferrugena
24 II. CHEMICAL CLASSIFICATIONS
substrate with Pénicillium sp. In actuality, 2ß-hydroxylation of progesterone (to-gether with 16a-hydroxylation) was among the first hydroxylations which were carried out (P-716, P-718), though no assignment was made until recently (Ap-42).
3-Hydroxylation. No hydroxylation at the 3-position had been described until very recently, when Cherry, Jones, and Meakins (Ap-12) reported the 3ß,12ß-dihy-droxylation of 5-androsten-7-one by Calonectria decora. Since all naturally occur-ring steroidal raw materials are oxygenated at the 3-position, the problem has had only academic implications.
4-Hydroxylation. No hydroxylation at the 4-position has been reported.36 The usual substrates for microbial transformations are A4-3-ketosteroids. The double bond at the 4-position interferes with normal modes of hydroxylation, accounting for the bulk of the experience to date. Saturated substrates might reasonably be hydrox-ylated at the 4-position with appropriate microorganisms. Substrates of the 3-keto-5ß-pregnane series might be preferred since their normal mode of enolization is to-ward the 4-position, thereby offering the possibility of more than one mechanism of hydroxylation.
5o?-Hydroxylation. One organism has been reported to cause 5a-hydroxylation. Pan and co-workers (P-706a) described the 5a-hydroxylation of A-nor-5a-pregnane-2,20-dione by Cokeromyces recurvatus. The paucity of observed 5a-hydroxylations is probably a function of the infrequent use of 5a-steroids as substrates.
5ß-Hydroxylation. Hydroxylation at the 5ß-position is limited to the 5ß-hydrox-ylation of cardiac aglycones (e.g., digitoxigenin) with Absidia orchidis, and was dis-covered by Nozaki (N-679).
others
36Cherry, Jones, and Meakins (Ap-12) have recently made a tentative assignment of 4ß,12ß-dihydroxylation to one of the products from the action of Calonectria decora on 5-andro-sten-7-one.
others
CLASSES OF CHEMICAL REACTIONS 25
6û!-Hydroxylation. No microorganism is known to cause enzymatic 6a-hydrox-ylation.37 Mallett, Fukuda, and Guynes (Ap-45; see also M-536, M-537) described the transformation of 3/3-hydroxy-5-androsten-17-one into 6a(and 6ß-)-hydroxy-l,4-androstadiene-3,17-dione with Actinoplanes mis sour iensis. These transformations depend on the nonenzymatic oxygénation of 5-androstene-3,17-dione, a reaction inter-mediate. Actinoplanes missouriensis seems to be deficient in Δ5-isomerase, which is an uncommon situation.
o o
Bridgeman and associates have mentioned the transformation of 5Œ-androstan-17-one into the 1β, 6α -diol by an unnamed organism in connection with structural studies of the product thus formed (Ap-6).
26 II. CHEMICAL CLASSIFICATIONS
6ß -Hydroxylation. One of the most common transformations is 6ß-hydr oxy la -tion. It is often, though not always, associated with 11a?-hydr oxy lation, 14a:-hydrox-ylation, or 17 a-hydr oxy lation. Peterson, Murray, and their collaborators discovered that Rhizopus arrhizus transforms progesterone into 6/3,11 a -dihydr oxy progesterone (M-601, M-616, P-729), 17a-hydroxyprogesterone into 6/3,17a-dihydroxyprogesterone (M-580), and Compound S into 60,17a,21-trihydroxy-4-pregnene-3,2O-dione (M-601, M-615, P-725). They reported the action of many other genera of the order
CH, I 3
c=o
Rhizopus arrhizus
Mucorales on a variety of steroidal substrates, observing 6/3-hydr oxy lation as a fre-quent occurrence (M-601). From our own experience, corticosteroids and their ana-logs (e.g. , prednisone) are 6/3-hydroxylated efficiently by Chaetomium sp. (C-108).
7 or-Hydr oxy lation. This transformation was first seen by Meystre, Vischer, and Wettstein with Peziza sp. on deoxycorticosterone (M-585) and by Fried and asso-ciates with Phycomyces blakesleeanus on progesterone (F-285, F-286).
The questions of assignment of configuration at the 7-position have been reviewed thoroughly by Tweit, Goldkamp, and Dodson (T-1037). From their analysis of rota-tional data, together with appropriate chemical information, unambiguous assign-ments can be made.
7 ff-Hydr oxy lation. The first microbial hydr oxy lation, reported by Kramli and Horvath (K-474), was that at the 7 ξ-position by Proactinomyces sp. on cholesterol. Although this may have been 7/3, no unambigious assignment can be made. Kahnt and collaborators (K-433) reported the unequivocal 7/3-hydr oxy lation of 21-hydroxy-5a-pregnane-3,20-dione by Rhizopus sp. Some confusion, which crept into the later assignments of 7a- and 7/3-hydroxy-3-keto-Δ* -steroids, was resolved by Tweit, Goldkamp, and Dodson (T-1037).
CLASSES OF CHEMICAL REACTIONS 27
HCT v : v ^ -OH 8a-Hydroxylation. There is no 8a?-hydrogen in the normal steroid structure.
Considerations of mechanism therefore rule out 8a-hydroxylation as a reasonable event. With steroids of abnormal skeleton, bearing an Sa-hydrogen atom, there is no a priori reason for excluding the possibility of 8a-hydroxylation. Such a reaction remains to be discovered.
8ff-Hydroxylation. Kondo and his collaborators have observed the only 8/3-hydroxylation described thus far (K-472, T-1014), from the action of Cercospora melonis on Compound S. Earlier transformations, for which 8/3-hydroxylation was
proposed as one of several alternatives [ e . g . , Helicostylum piriforme on Compound S (M-601)], have since been shown to be 9a-hydroxylations.
9o-Hydroxylation. This transformation was observed first by Peterson and Murray (E-204, M-601) with Helicostylum piriforme on Compound S, although the choice of assignment between 8/3 and 9a was not made. Schubert and associates (S-815) developed chemical methodology from which a more precise assignment could be made and deduced thereby the 9a-hydroxylation or progesterone by Circinella sp.
Dodson and Muir provided the first completely unambiguous evidence for both position and configuration (D-172) in the 9a-hydroxylation of progesterone by Nocardia sp. The formation of the illustrated 3,9-oxide can only occur if the hydroxyl at the 9-position is a.
28 II. CHEMICAL CLASSIFICATIONS
The 9û!-hydroxylation has considerable theoretical and practical significance. Dodson and Muir (D-169 - D-171) recognized it as a key s tage in a major path of microbial degradation of the steroid nucleus. The cleavage of ring B results from a
spontaneous reverse aldol reaction, following 1-dehydrogenation and 9a-hydroxylation. Bacterial 1-dehydrogenating genera have, by and large, been shown to act also as 9a-hydroxylators. Examples include No car dia (D-172), Pseudomonas (D-171), Arthro-bacter, or Cor ynebac ter turn sp. (C-138, D-171), and others. As a consequence, an inherent hazard in the use of these cultures as 1-dehydrogenators for the preparation of synthetic adrenocorticoids and other hormonal agents has been the loss of product through 9o!-hydroxylation and degradation. This phenomenon has been attributed generically to a"destructase" (F-230), and techniques for suppression of the secondary reactions have been suggested. The quinonoid species used for this purpose probably act by suppressing 9a-hydroxylation (or the formation of the required enzyme).
It is probably also true that the many bacteria, which can use cholesterol (or steroids generally) as a sole carbon source, break down the steroid nucleus by approx-imately the same sequence of reactions. This will be taken up in greater detail in a later section devoted to degradation.
9/3-Hydroxylation. On mechanical grounds, steroids with conventional skeletons should not give this transformation. "Retro" steroids38 of the 9/3,10a?-configuration, however, could lead to 9/3-hydroxy products. Microbiological transformation studies with representative structures of this type have been made at the Phillips-Duphar Laboratories.39 In the light of the interesting hormonal activities found within this class (e.g., dydrogesterone-progestational agent) further developments may reasonably be anticipated. CH
I 3
Dydrogesterone
lQg-Hydroxylation. Some 19-nor steroids with the 10a-configuration have been prepared.40 These have yet to be oxygenated microbiologically.
38Westerhof, P . , and Reerink, E. H. , Rec. Trav. Chim. 7^, 771 (1960). 39French Patent 1,372,851 (Sept. 18, 1964); see also Ap-16. 40Wenger, R. , Dutler, H. , Wehrli, H. , Schaffner, K., and Jeger, O. , Helv. Chim.
Acta45, 2420 (1962).
CLASSES OF CHEMICAL REACTIONS 29
1 Off-Hydroxylation. Peterson, Murray, and their collaborators (M-642, P-708) described the 1Off -hydr oxy lation of 19-nortestosterone by Rhizopus nigricans. The major product, however, was lla,17ff-dihydroxy-4-estren-3-one. More recently,
DeFlines and co-workers (D-150) reported the efficient use of Botrytis paeoniae and other organisms for uncomplicated 1 Off-hydr oxy lation of the same substrate.
llq-Hydroxylation. One of the first hydroxylations described and also one of the most important for industry is lla-hydroxylation. Peterson and Murray discovered 11 a-hydr oxy lation by Rhizopus sp. and other members of the Mucorales order, using a wide variety of substrates (e.g., progesterone, 17a-hydroxyprogesterone,
Compound S), as part of a rational program to improve the synthesis of cortisone (M-601). This goal was realized through their work and that of the Levin and Hogg chemical groups at Upjohn. The hydrocortisone synthesis via the 11 a-hydr oxy lation of progesterone remains the cornerstone of the most efficient method for the prepara-tion of a variety of natural and synthetic adrenal hormones. The price of natural glucocorticoids has fallen from in excess of $200/gram (1949) to about $0.45/gram (1965) as a result of the perfection of both the chemical and microbiological stages of the hydrocortisone synthesis.
Subsequently, it was shown that lla-hydroxylation is one of the most common transformations. The better cultures may be identified in Table I, "Transformation by Products," by the high yields recorded for the illustrated conversions (e.g. , 11a-hydroxylated products in the C21H30O3, C21H30O4, and C21H30O5 series).
1 Iff-Hydr oxy lation. Although many claims for llff-hydroxylation are made in the literature, very few organisms afford a clean reaction in high yield. The first recorded llff-hydroxylation, by Colingsworth, Brunner, and Haines (C-134), was the transformation of Compound S into hydrocortisone with Streptomyces fradiae. The yield with this organism was very low. The first practical llff-hydroxylation pro-cesses were those of Shull, Kita, and Davisson (S-871, S-875) using Curvularia lunata and those of Hanson, Mann, and co-workers (H-339; M-556) using Cunninghamella blakesleeana. The former has continued to be important for the commercial produc-tion of hydrocortisone from Compound S, as practiced by Charles Pfizer, Inc. and its licensees (particularly Schering A. G. ). In contrast with the liai-hydr oxy lation of progesterone by Rhizopus nigricans, which affords yields in excess of 90%, llff-hydroxylation of Compound S by Curvularia lunata has rarely been reported to be better than 60-65%. Further improvement of this yield or a related llff-hydroxylation would have significant consequences for industry.
30 II. CHEMICAL CLASSIFICATIONS
12ohHydroxylatioa This rare transformation has been seen in our laboratories^ also by Fried and Thoma and by Kondo and Tori in rather special cases. We observed that testosterone was transformed into 12a,17/3-dihydroxy-4,14-androstadien-3-one in very low yield by Wojnowicia graminis (H-381). The presumed precursor of the 12a?-hydrox-ylated product is the 12a,14o!-diol (in view of the formation of 14a-hydroxy-4-andro-stene-3,17-dione in the fermentation). The required elimination of the 14a-hydroxy
+ others products
group to give the Δ14-unsaturation is logically, though not necessarily, an artifact from the processing of the fermentation. Fried and Thoma (F-277) observed that fermentation of 9(ll)-dehydroprogesterone with Colletotrichum phomoides, Tham-nidium elegans, or Aspergillus nidulans gave 6/3,12a-dihydroxy-4,9(ll)-pregnadiene-3,20-dione as a major product. This product was transformed in part into the corre-sponding 9/3,llj3-oxide, presumably through the action of an 11/3-hydr oxylating enzyme. Kondo and Tori (K-473) reported the 12a-hydr oxylation of 9a-hydroxy-4-androstene-3,17-dione by Cercospora melonis. The same culture also transformed 4-androstene-3,17-dione to the same 9a,12a-dihydroxy product.
+ others products
12/3 -Hydr oxylation. First reported by A. Schubert, Siebert, and collaborators by the action of Calonectria decora on progesterone and 15a-hydroxyprogesterone (S-814; see also S-810, S-816, S-817), this transformation remains infrequent with conven-tional 3-keto-A4-steroidal substrates (D-152, T-1036). The reaction is somewhat
ÇH3
c=o
C. decora
ΌΗ ΌΗ
CLASSES OF CHEMICAL REACTIONS 31
more common with cardiac aglycone substrates. The earliest examples of the latter were described by Gubler and Tamm (G-320, T-977, T-979) and include the 12/3-hydroxylation of digitoxigenin to digoxigenin by Fusarium lint.
Hydroxylation at the 15a-position often co-occurs with that at the 12/3-position.
13-Hydroxylation. No studies with 13-demethylsteroids have been reported. 14o?-Hydroxylation. The earliest example of 14a?-hydroxylation was reported
by Murray and Peterson (M-601) with Helico s tylum piriforme on Compound S. This transformation is quite common with progesterone, deoxycorticosterone and Com-pound S. Mucor sp. are among the more effective 14oi-hydroxylators (E-204, M-614, M-635, T-980).
CH2OH
C=0
CH?0H I 2
C=0
-f others
14/3-Hydroxylation. No reports of transformations with steroids bearing a 14/3-H (C-D eis ring fusion) have been recorded. Cardiac aglycones customarily contain a 14ß-hydroxyl group. Microbiological conversion studies with 14β,17αι-progesterone or a related substrate might conceivably lead into the former ser ies .
15 a -Hydroxylation. This hydroxylation was discovered by Fried and colleagues with Colletotrichum antirrhini on progesterone (F-285, F-287, F-288) and by Meystre, Vischer, and Wettstein with Gibberella baccata on deoxycorticosterone (M-585, U-1043, W-1087). It can be accomplished efficiently with a variety of substrates (B-58, C-139, D-158, G-319, T-980).
32 II. CHEMICAL CLASSIFICATIONS
15/3-Hydroxylation. The first reports of 15/3-hydroxylation were from Fried and associates with Phycomyces blakesleeanus on progesterone (F-285 - F-288) and from Meystre, Vischer, and Wettstein with Lenzites abietina on deoxycorticosterone (M-585, W-1087). The 15/3-hydroxylation of Compound S goes especially well with Bacillus megaterium (H-382).
CH90H I c=o
CH?OH I c=o
16a -Hydroxylation. One of the earliest examples of microbial hydroxylation, reported by Perlman, Titus, and Fried (P-718) in 1952, was the 16a-hydroxylation of progesterone by an actinomycete later shown to be Streptomyces argenteolus. This
5. argenteolus^
CH, I 3
C=0
ΌΗ others
class of hydroxylation has been studied carefully subsequent to the discovery of triam-cinolone, a widely used antiinflammatory steroid. (The manufacture of triamcinolone incorporates more microbiological manipulation than that of any other steroid presently in commerce.) Many streptomycetes (e.g. , S. roseochromogenus) are not very sub-strate specific, 16a-hydroxylating a wide range of steroids from testosterone (F-288) and 1-dehydrotestololactone (P-706, T-1000), on the one hand, to 9a-fluorohydrocor-tisone (G-297, S-912, T-1002), on the other, with good efficiency in many instances.
5. roseochromogenus^
CLASSES OF CHEMICAL REACTIONS 33
CHo0H
C=0
CHLOH
S. roseochromogenus
16ff-Hydroxylation. This transformation has been seen infrequently. It was reported from our laboratory using Wojnowicia graminis with testosterone (H-381). Dodson and Mizuba (D-166) have described the 16/3-hydroxylation of androstenedione
(minor) (major)
with Corticium centrifugum. In their discussion they make the point that introduction of the 160-hydroxyl group in their (and our) case cannot be ascribed unambiguously to a 160-hydroxylation reaction. They suggest the illustrated, alternative path, which proceeds via 16a-hydroxylation, rearrangement, and reduction. Evidence for this
C centrifugum^
proposal is that the 16-keto-17/3-hydroxy intermediate (I) was isolated from the fer-mentation by Dodson and Mizuba. In our case, all the intermediates between testos-terone and 16/3-hydroxytestosterone required by the Dodson-Mizuba proposal were isolated from the reaction mixture.
Nawa and co-workers (N-651) have described the 16/3-hydroxylation of digitoxi-genin to gitoxigenin by Helicostylum piriforme. Identification was by paper chroma-tography. This example cannot be accommodated within the Dodson-Mizuba proposal.
(I)
others
34 IL CHEMICAL CLASSIFICATIONS
17o?-Hydroxylation. This transformation was considered at one time to have potential importance as a stage in the preparation of adrenocorticoids bearing the dihydroxyacetone side chain. Meystre, Vischer, and Wettstein (M-584) described the 17a-hydroxylation of deoxycorticosterone by Trichothecium roseum. A strain of the same culture with similar properties (Cephalothecium roseum) was reported at
CHo0H
about the same time by Meister and co-workers (M-581). The Meister culture was distinguished from the Meystre culture by its ability to lla-hydroxylate also.
In practice, chemical methods of 17a-hydroxylation have turned out to be supe-rior to microbiological methods. This fact, combined with the relative rarity of 17a-hydroxylating species, has led to neglect of serious study of this reaction, and it is not employed for other than research applications today.
17/3-Hydroxylation. Substrates with which this reaction might be observed have not been studied. There has been little incentive to look for this reaction since good chemical methods are available for the synthesis of 17/3-hydroxy-17a-pregnanes and 17/3-hydroxyandrostanes.
18-Hydroxylation. For a time some interest was attached to the search for an 18-hydroxylator. After Reichstein and co-workers4 1 showed that aldosterone, one of the adrenal hormones regulating salt metabolism in the human, was substituted at the
CI-LOH OH I
Aldosterone
18-position, a convenient synthetic route to this compound was sought. Several bril-liant and versatile chemical solutions to the problem were found, which have resulted
4 1 Simpson, S. A. , Tait, J . F . , Wettstein, A. , Neher, R. , von Euw, J. and Reichstein, T . , Helv. Chim. Acta 37^ 1200 (1954).
Schindler, O. ,
CLASSES OF CHEMICAL REACTIONS 35
in greatly diminished interest in this potential application for microbiological t rans-formations. Kondo and Tori (K-473) reported the first 18-hydroxylation with Cerco-spora {Corynespora) melonis on androstenedione and 9a-hydroxyandrostendione.
+ others
Kondo, Mitsugi, and Tori (Ap-38) extended this finding to develop a synthesis of aldosterone, using Corynespora cassiicola.
(I)
CHo0H
C=0
(II) Aldosterone
The conversion of 18-hydroxycorticosterone (I) into the 11,18-oxide (II) was accomplished by chemical means. This step, taken together with the two microbio-logical stages, completes a novel partial synthesis of aldosterone from corticosterone.
19-Hydroxylation. Hasegawa and Takahashi (H-347) first described the 19-hydroxylation of Compound S with Corticium sasakii. The structure was established by Hagiwara (H-326). This hydroxylation remains quite r a re .
The 19-hydroxylation process has become an object of renewed interest in the light of the findings of Sih concerning the efficient microbial conversion of 19-hydroxy-cholesterol 3-acetate to estrone. Excellent chemical methods, however, which were developed during the search for techniques of 18-oxygénation, exist for the introduc-tion of the 19-hydroxyl group. It is unlikely that microbiology will make an important contribution to this aspect of the new estrone technology.
36 II. CHEMICAL CLASSIFICATIONS
CHL0H I 2
Hydroxylation at the 20- and 22-positions and beyond. The 20-position is usually occupied by a carbonyl group in the commonly employed pregnane substrates and is thereby not available for reaction; C-22 and beyond are absent. With the work of Sih, interest has revived in C^ and higher sterol substrates.
Working with two Nocardia sp . , Sih has shown that cholesterol is degraded by fission between C-24 and C-25, C-22 and C-23, and C-17 and C-20.410
One may speculate that hydroxylations at C-26 and perhaps at C-24 and C-22 are involved in the degradative sequence, although Sih has not chosen to reach these conclusions as yet, nor is there any evidence in their support. His evidence and pro-posals are discussed in greater detail in the section on degradation.
Mammalian hydroxylations of cholesterol at C-20 and C-22 have been demon-strated .41& It would not be surprising to find microorganisms with the same capaci-t ies.
21-Hydroxylation. Just as 17a-hydroxylation is of interest for corticoid syn-thesis, so too is 21-hydroxylation. Here again, excellent chemical methods were available for oxygénation which inhibited any continuing, deep study of this problem. The microbial process was first shown by Meystre, Vischer, and Wettstein (M-584) using Ophiobolus herpotrichus on progesterone and 17a-hydroxyprogesterone, among
others. This hydroxylation was later applied to the total synthesis of aldosterone, as an ingenious method of simultaneously introducing the required 21-oxygen function and resolving the d,l -mixture (W-1102). Only the natural form of the starting material was transformed.
0. herpotrichus , L- starting material
4 1 0 Sih, C. J . , Wang, K. C. , and Tai, H. H. , J . Am. Chem. Soc. 89, 1956 (1967); Sih, C. J . , Tai, H. H. , and Tsong, Y. Y. , ibid., p. 1957.
4lb Chaudhuri, A. C. , Harada, Y. , Shimizu, K., Gut, M. , and Dorfman, R. I . , J . Biol. Chem. 237, 703 (1962).
CLASSES OF CHEMICAL REACTIONS 37
Dehydrogenation
Following the discovery of 1-dehydrogenation by Fried, Thoma, and Klingsberg (F-284) and Vischer and Wettstein (V-1056), alternative formulations of the path for this reaction were presented (V-1053, W-1087). Levy and Talalay, from studies with
the dehydrogenating enzyme mixture isolated from Pseudomonas testosteroni, con-cluded that direct dehydrogenation (no intermediate hydroxylation) is the most probable path with this organism (L-509). The evidence was that the in vitro dehydrogenation reaction did not require oxygen, whereas the enzymatic hydroxylation process with steroids has been shown to require oxygen. They also demonstrated that phenazine methosulfate is an efficient oxidizing agent for A4-3-ketosteroids, when acting in concert with an enzyme preparation from Pseudomonas testosteroni under anaerobic
conditions.42 These results, together with the observations of Levy and Talalay that suitable l a - and lß-hydroxylated substrates (e.g. , la-hydroxy-4-androstene-3,17-dione) were not converted to 1-dehydro species with the same enzyme mixture in the presence of phenazine methosulfate, can be taken to affirm the dehydrogenation mech-anism and to exclude the hydroxylation-dehydration mechanism.
The dehydrogenation mechanism is also supported by the work of Gale and asso-ciates (G-291). They showed that Bacillus sphaericus contained a quinone, character-ized by them as vitamin K2(35), which was essential for the dehydrogenation of hydro-cortisone to prednisolone. In a cellfree preparation derived from B. sphaericus, photoinactivation of vitamin K2(35) destroyed the dehydrogenation power of the system. The system was reactivated fully by the addition of vitamin K2(35) or related quinoid structures (e.g. , menadione or hexahydrocoenzyme Q). Gale and collaborators con-cluded that vitamin K2(35) is the cofactor for dehydrogenation with B. sphaericus.
Other oxidizing agents which were ineffective in this system were NAD, NADP, ribo-flavin monophosphate, FAD, ferricyanide ion, and cytochrome c. The inference should not be made that in vivo transformation with Ps . testosteroni can be run anaerobically with any degree of efficiency. Since the necessary oxidizing reagent species are rarely present in stoichiometric quantities, oxygen is required to regenerate the natural equivalent(s) of phenazine methosulfate.
38 II. CHEMICAL CLASSIFICATIONS
cellfree preparation of B. sphaericus
^ Ö > t +
Rm
OH
OH
^ R
^ R
From his studies with Ps. testosteroni, Talalay43 favors the views that flavins are required intermediates in the oxidation-reduction chain and that they are truly coenzymatic, whereas quinones are, more likely, secondary oxidizing agents, playing their role later in the oxidation-reduction cycle. For the present, at least, there is no evidence for a unity of mechanism in the diverse microbialdehydrogenation processes.
Most recently, Iida and colleagues (Ap-31) have prepared a cellfree enzyme sys-tem with reversible A^hydrogenase-dehydrogenase activity. The enzyme mixture was isolated from cultures of Bacterium cyclo-oxydans, and the production of enzyme was promoted by the addition of steroidal inducers (e.g. , l,4-androstadiene-3,17-dione).44
The dehydrogenation reaction was stimulated by a quinone (menadione) and hydrogéna-tion by NADH. The activities could not be separated by enzyme fractionation techni-ques. Further detailed studies with B. cyclo-oxydans might throw more light on dehy-drogenation mechanisms.
The stereochemistry of the microbial dehydrogenation process at the 1- and 2-positions has been studied with one microorganism, Bacillus sphaericus, by Ringold, Hayano, Stefanovic, and co-workers (H-373, R-769). The relevant indirect evidence is that substrates with Iß- or 2a-substituents are dehydrogenated successfully by B. sphaericus, whereas those with l a - or 2/3-substituents are not. From these findings
R = OH or CH
it was inferred that the l a - and 2/3-hydrogen atoms are required for the microbial dehydrogenation to take place (H-373).
This conclusion was supported by the observation (R-769) that 1/3-deuterium largely survives the dehydrogenation process, whereas la-deuterium is lost.
B. sphaericus cellfree enzyme preparation
43 Talalay, P . , Ann. Rev. Biochem. 34, 347 (1965). 44 The ability of B. cyclo-oxydans to produce both hydrogenase and dehydrogenase activity
was first recognized by Goodman, May, and Smith (G-296).
CLASSES OF CHEMICAL CLASSIFICATIONS 39
Ringold, Hayano, and Stefanovic then proposed that the dehydrogenation process takes place via the illustrated reaction sequence, the first step of which is the enzyme-mediated enolization of the 3-ketone toward the 2-position. This is followed by hydride transfer of the α-hydrogen at the 1-position to the coenzyme, with subsequent collapse
+ Enz + Coenz H
of the enzyme-substrate complex. That enolization occurs readily in the fermentation medium was established by isotope exchange studies. This evidence was then used to support the contention that enolization is a necessary stage in the dehydrogenation pro-cess. The failure of the attempted dehydrogenation of 5/3-androstane-3, 17-dione by B. sphaericus, in contrast to the successful dehydrogenation of 5a-androstane-3,17-dione, was explained in terms of the normal modes of enolization of the two substrates. The former enolizes toward the 4-position and thereby fails to provide the necessary intermediate for elimination of the hydrogen at the lo:-position. The latter enolizes toward the 2-position, leading to the completion of the anticipated reaction.
A subsequent refinement of this proposal has been made by Jerussi and Ringold (Ap-33). The crux of the refinement is that the enzyme which promotes enolization is also implicated in the oxidation-reduction process, in that it has bound to it a flavin or some other redox system, which acts to abstract hydride ion from \a as the second stage of the process. Jerussi and Ringold illustrated the reaction system as follows:
c·
Enz
V.
-H
• H · ^ A - H
( A = proton donor, B= proton acceptor, C= hydride acceptor )
The conclusions were derived from the study of deuterium isotope effects on reaction rates at the la- and 2/3-positions.
These proposals are very satisfying in many ways. An obstacle, however, to the extension of the proposed mechanism to all microbiological dehydrogenation of 3-ketosteroids at the 1-position is the work of Fonken and Murray (F-253). They showed that the 20-ketal of 5ß-pregnane-3,ll,20-trione is dehydrogenated at the 1-position by Septomyxa affinis. Either the illustrated 3-keto-5/3-pregnane (I) enolizes abnormally
40 II. CHEMICAL CLASSIFICATIONS
(I) AO
(toward 2- instead of toward 4-), or the Ringold-Hayano-Stefanovic proposal does not extend to S. affinis and organisms which behave like it. This qualification applies only to the enolization part of the hypothesis for the time being. It might be desirable to establish the direction of enolization of the 3-ketone in (I) . A more ambitious under-taking, which could be justified if enolization is indeed toward the 4-position, would be to show the stereochemistry of hydrogen abstraction in the Fonken-Murray case by appropriate labeling techniques.
Sites of Reaction. Dehydrogenation has been reported at the 1-, 4-(5a- and 5ß-), 7-, 9(11), 14-, and 16-positions. The dehydrogenation reaction was described first by Horvath and Kramli in 1947 (H-406, H-407) for the conversion of cholesterol into 7-dehydrocholesterol with Azotobacter sp. No other examples of this reaction have been
reported, and this method is of significance only as a milestone in the evolution of microbial transformations.
In 1953, after the resurgence of interest in the field, Fried, Thoma, and Klings-berg (F-284) and Vischer and Wettstein (V-1056) discovered the 1-dehydrogenation reaction. The former, using Cylindrocarpon radicicola with progesterone, testos-terone, and Compound S showed that in all instances 1-denydrotestololactone was
o o II , II
R = 0H(R '=H) , R = C-CH_ (R' = H ) , R = C-CH 0H(R' = 0H)
formed in about 50% yield. Streptomyces lavendulae, with progesterone, on the other hand, gave a mixture of 1,4-androstadiene and 17/3-hydroxy-l,4-androstadien-3-one.
CLASSES OF CHEMICAL REACTIONS 41
Vischer and Wettstein reported the use of Fusarium solani and Fusarium cau-casicum to dehydrogenate 4-androstene-3,17-dione and related C19 species to 1,4-
androstadiene-3,17-dione. Progesterone and deoxycorticosterone were also dehydro-genated and degraded to the same product. Saturated substrates and 3/3-hydroxy-A5-
steroids were transformed to l,4-androstadiene-3,17-dione, as well, but in poorer yield. Wix and Albrecht (W-1116, W-1118) investigated the use of F. caucasicum as a practical tool for the preparation of l,4-androstadiene-3,17-dione, which has been an important precursor in the manufacture of estrone.
After the discovery of prednisone and prednisolone through the use of Coryne-bacterium simplex (N-671) with cortisone and hydrocortisone, respectively, many 1-dehydrogenating cultures were described. Among the most significant of these were Bacillus sphaericus (S-942), Bacterium cyclo-oxydans (K-480),and Septomyxa affinis (M-573), all of which have been or are being used for the manufacture of antiinflam-matory steroids.
In general, preferred substrates for 1-dehydrogenation are A4-3-ketosteroids. Saturated 3-ketosteroids have also been used, but chemical methods of dehydrogena-tion are usually superior to microbial methods for these substrates.
42 II. CHEMICAL CLASSIFICATIONS
The 1-dehydrogenation reaction is also a very convenient way to aromatize a 19-nor steroid (C-128, H-386). Ordinarily, the reverse sequence has been the
o-^K o<^K> economically significant one, insofar as phenols have been the precursors of 19-nor-steroids. The total synthesis of 19-norsteroids, however, by Velluz and his collabo-rators at Roussel45 has made these compounds available by a route independent of aromatic antecedents. Hence the microbial synthesis of steroidal phenols can become more than academic.
Dehydrogenation at the 4-position was first described by Vischer and Wettstein (V-1056) with the conversion of 5o?-androstane-3,17-dione and related species into l,4-androstadiene-3,17-dione by Fusarium solani. This class of transformation has
also been reported in the pregnane series by Stoudt and associates (S-943) with No cardia blackwellii and by Coronelli, Kluepfel, and Sens i (C-138, K-451) with Corynehacterium simplex, and in the bile acid series by Hayakawa and collaborators (H-359, H-365, T-975) with Streptomyces and Corynehacterium sp. The work of Coronelli, Kluepfel, and Sensi raises an interesting problem. In each of the illus-trated cases the A-ring saturated substrate is transformed into a 1,4-diene46 as the
CHoOH
45Chem. Eng. News 42 ,̂ 42 (1964). 46 With concomitant 9a, lla-epoxidation of the Δ 9 ' 1 1 substrate.
CLASSES OF CHEMICAL REACTIONS 43
major product. With 16/3-methyl-17o!,21-dihydroxy-5a!-pregnane-3,ll,20-trione, the minor product is the monounsaturated Δ1-compound, which is implicated as an inter-mediate in the formation of the 1,4-diene (K-451). From 16/3-methyl-17o!,21-dihy-droxy-A9(11)-5a-pregnene-3,20-dione 21-acetate, the products of dehydrogenation are the Δ1?4- and the Δ4-species. The Δ4-species might be formed either as a pri-mary product of reaction from the A-ring saturated substrate or as a product of re -duction of the ΔΜ-diene (G-296). If the former were true, it would present yet another dilemma with which the enolization hypothesis of the microbial dehydrogena-tion process must contend.
Dehydrogenation at the 9(11)-position has been reported from the action of Glomerella fusaroides on estrone (L-494). Glomerella is orginarily a good hydrox-ylating species, with no hint of dehydrogenating activity. The course of this dehydro-genation, which is also accompanied by a bizarre inversion at the 14-position, r e -mains to be clarified.
We observed dehydrogenation at the 14-position with Wojnowicia graminis on testosterone (H-381), together with 12ce-hydroxylation. It is our view that this is not a true dehydrogenation, but is an artifact arising from prior formation of the 12o!,Ha'-diol,47 followed by elimination (not necessarily enzymatic) of the labile 14 a?-hydroxyl. The driving force for the postulated elimination may come from the 1,3-diaxial inter-action of the hydroxyl groups at 12a and 14a.
Dehydrogenation at the 16-position by Trichothecium roseum on digitoxigenin has been reported (T-1013). Since this organism is normally a 17ai-hydroxylator, the question remains whether the 17o?-hydroxy derivative of digitoxigenin is the precursor of the observed product.
Epoxidation
Bloom and Shull deduced the generalization that microorganisms which can cause axial hydroxylation at a given carbon atom can also cause epoxidation of a double bond attached to the same carbon atom (B-66). The epoxide oxygen will have the same configuration as the hydroxyl group which is normally introduced at the saturated carbon atom. Their explanation of this thesis was that the pi electrons of the double
bond assume an orientation similar to that of the electrons of the axial C,H bond and that the hydroxylating enzyme does not differentiate between the two situations. The initial stage of reaction, namely attack by oxygen (originating in the gas phase), is the same for hydroxylation and epoxidation. The natures of the transition state and any reaction intermediates remain to be elucidated.
Sites of Reaction. Bloom and Shull (B-66) showed that Curvularia lunata epox-idized 17a,21-dihydroxy-4,9(ll)-pregnadiene-3,20-dione to the 9/3,11/3-epoxide and
14a-Hydroxy-4-androstene-3,17-dione is also a product of the same fermentation.
XX
44 II. CHEMICAL CLASSIFICATIONS
17a,21-dihydroxy-4,14-pregnadiene-3,20-dione to the 14a,15a-epoxide. They also indicated that other known axial hydroxylators at the 11-position (Cunninghamella blakesleeana) and at the 14-position (Helicostylum piriforme, Mucor griseocyanus, etc. ) also formed epoxides with the appropriate substrates.
Prochazka and colleagues (P-741) have reported the formation of a 5,6-oxide of unspecified configuration from the action of Rhizopus nigricans on 3/3-hydroxy-B-nor-5-androsten-17-one. Based on the known ability of Rhizopus sp. to 6/3-hydroxylate, we think the oxide must be 5/3,6/3. This is consistent with the observed formation, in
other products
the same transformation, of a5a,6/3-dihydroxy product, which probably arises from the diaxial opening of the oxide with water (possibly enzymatic; cf. C-87).
From the action of Nocardia sp. on Δ 9 ( 1 1 ) compounds, 9a, liai -epoxides have been formed (S-886). This is attributable to the 9a-hydroxylating ability of Nocardia.
Corynebacterium simplex behaves in a similar fashion (C-138). Kurosawa, Hayano, and Bloom (K-484) reported the 11/3,12/3-epoxidation of 4,ll-pregnadiene-3,20-dione with Curvularia lunata.
CLASSES OF CHEMICAL REACTIONS 45
C. lunata
CH, I 3
C=0
In general, chemical methods of epoxidation are superior to the microbiological. The principal significance of the latter has been to provide a better understanding of the chemical mechanism of the microbial oxygénation process. Oxidation of Alcohols to Ketones or Aldehydes
The oxidation-reduction process for the conversion of hydroxysteroids to keto-steroids (and the reverse reaction) has been studied in detail by Talalay and his col-laborators48 with induced enzymes isolated from Pseudornonas testosteroni. They purified one enzyme system which oxidized the 3a-hydroxyl group and another which oxidized both 3/3- and 17/3-hydroxyl groups. Talalay has characterized the oxidation-reduction reaction with these enzymes as NAD-linked and illustrated the general r e -action as:
-OH NAD enzyme \
-T. " C = 0 + NADH -I- H
There is little substrate specificity among microorganisms producing hydroxy-steroid dehydrogenases. The only limitation which is usually found is that the formal stereochemistry and position of the hydroxyl group to be oxidized should be the same as that in the model from which the proposed transformation is derived. For example, 3a-hydroxysteroid dehydrogenase studied by Talalay is effective irrespective of whether the 3a-hydroxyl group is axial or equatorial. The same is also true for the 3/3-hydroxysteroid hydrogenase.
There is some evidence from the work of Ringold and collaborators with Pseudo-rnonas testosteroni that the presence of electron-withdrawing groups at the 6-position in 3-keto-A4-substrates shifts the direction of net change (and hence the equilibrium) from oxidation to reduction. From these results it may be inferred that electron density at the carbonyl group can be decisive in determining equilibrium. This is also consistent with the formulation of the oxidation-reduction process as hydride ion transfer between diphosphopyridine nucleotide and substrate.49 These findings are discussed in greater detail in the section on reduction of carbonyl groups.
48 Talalay has reviewed his work in extenso, in "The Enzymes" (P. D. Boyer, H. Lardy, and K. Myrbäck, eds.) 2nd ed. , Vol. 7, p. 177. Academic P ress , New York, 1963.
4 9 H. R. Levy, P. Talalay, and B. Vennesland [Progr. Stereochem. 3̂ , 299 (1962)], have reviewed the evidence for the chemical change in NAD+ which accompanies the oxidation of an alcohol to a ketone or aldehyde.
XH„
R
II C-NH,
H J .C—NH,
46 II. CHEMICAL CLASSIFICATIONS
Useful oxidation of alcohols to ketones has been known since the work of Bertrand in 1896.8"10 The application of this reaction to steroid chemistry was first made by Mamoli and his collaborators (S-808, V-1047), who showed that 5-androstene-3/3,17/3-diol could be oxidized to 4-androstene-3,17-dione with bacteria isolated from contam-inated yeast. The same crude culture also oxidized 5-pregnen-3/3-ol-20-one to
progesterone (M-540). Various pure strains identified as Micrococcus dehydrogenans (E-215), Corynebacterium mediolanum (A-l, M-546), and Flavobacterium dehydro-genans (N-688, N-689) have been very useful in the laboratory for the oxidation of the 3/3-hydroxyl group, often together with deacetylation at the 3-position (and elsewhere) and isomerization of a double bond at the 5- to 4-position. This technique remains the method of choice for combined deacetylation-oxidation-isomerization (3/3-acetoxy-Δ5— 3-keto-A4) in the presence of oxidation-sensitive or pH-labile groups elsewhere in the molecule.
Oxidations of hydroxyl groups have also been observed at the 3a*- (S-799, S-800, S-818, S-943), 6/3- (B-32), 7a«- (S-799, S-800), 11/3- (H-344, M-556), 12a-(S-799, S-800, S-810), 15/3- (T-1036), 16a?- and/or 16/3- (S-793a), 18 (Ap-38), and 20/3-positions (C-128, N-665). In general, chemical methods of oxidation have been preferred for reaction at these sites.
The many instances of apparent direct introduction of carbonyl groups at unsub-stituted sites are almost certainly hydroxylation followed by oxidation. There are as yet no grounds for believing that a mechanism exists for the direct transformation of the méthylène group into carbonyl by microorganisms. Oxidation of Ketones to Esters and Lactones
The microbiological counterpart of the Baeyer-Villiger oxidation of ketones to esters or lactones was discovered by Fried, Thoma, and Klingsberg (F-284) and Peterson, Murray, and co-workers (P-726). Fried and his co-workers appreciated the parallel with the Baeyer-Villiger reaction and suggested correctly the sequential nature of the degradation of progesterone into testololactone by Pénicillium chryso-genum. Using Streptomyces lavendulae with progesterone, Fried was able to isolate
? H,
C=0 I 0
OH
P. chrysogenum · ■■
also other Penicillia and Aspergilli (P-726)
(I) (2)
(3)
CLASSES OF CHEMICAL REACTIONS 47
17/3-hydroxy-l,4-androstadien-3-one (equivalent to stage 2) and 1,4-androstadiene-3,17-dione (equivalent to stage 3). He also observed that the presence of the 17a-hydroxyl group in a 20-ketopregnane did not prevent the reaction (e.g., Cylindrocarpon radicicola with Compound S).
ChLOH 1 2
Ά c=o irOH
1 C. radicicola
j -V
\
_ J
CH, Ί 1 3
c~o ! i 1
^
0
J
/°γ°
Fonken, Murray, and Reineke (F-254) isolated testosterone acetate (stage 1) from the degradation of progesterone with Cladosporium resinae, thereby substanti-ating further the thesis of Fried, Thoma, and KLingsberg. They proved unequivocally, with appropriately labeled progesterone, that the 21-carbon atom of progesterone is the precursor of the methyl carbon atom of acetate in testosterone acetate.
Prairie and Talalay (P-737) showed that the ether oxygen of testololactone (as distinct from carbonyl oxygen) is provided by oxygen from air in the transformation of testosterone into testololactone by P. lilacinum (P-726).
If one makes a judicious choice of organism and fermentation conditions, any of the intermediates between progesterone and testololactone (or 1-dehydrotestololactone) may become a major product. The potential value of this degradative technique was appreciated in the early, independent report of Vischer and Wettstein (V-1056) con-cerning the degradation of progesterone into l,4-androstadiene-3,17-dione by Fusarium sp. They proposed that a more efficient synthesis of estrone than the one employing dehydroepiandrosterone as starting material might incorporate the proges-terone degradation as a key stage. This possibility was investigated in some detail by Wixand Albrecht (W-111Ç W-1117,W-1118) using Fusarium solani In the final analysis, the purely chemical routes to androstadienedione and estrone have been more econom-ical, although the question has been reopened again recently by the findings of Sih con-cerning the microbial degradation of 19-hydroxycholesterol. Oxidation of Sulfides to Sulfoxides
This reaction has been reported by Holmlund and co-workers (H-405) and Dod-son and Soliman (D-174, D-176). Holmlund converted 17/3-hydroxy-7o?-thiomethyl-4-androsten-3-one 17-acetate into the corresponding deacetylated 7a-sulfoxidomethyl compound by the action of Calonectria decora. Dodson and Soliman described the
48 II. CHEMICAL CLASSIFICATIONS
transformation of 17a-thiomethyl-4-androsten-3-one into two sulfoxides (and an 11a-hydroxylated sulfoxide) whose configurations differed at sulfur. Nothing is known about the mechanism of this reaction, but it is reasonable to suppose that the entering oxygen is provided by air .
CH, I 3
Oxidation of Amines to Ketones
Only one example of this interesting and possible useful transformation has been reported. DeFlines and co-workers (D-148) described the conversion of conessine to A4-conenin-3-one by Gloeosporium cyclaminis and Hypomyces haematococcus. Rich sources of 3-aminosteroids have been found in the Funtumia sp. of African plants.50
HX.
H.O 3 " ^
— C H ,
While no evidence has been adduced in support of a mechanism for this reaction, one may speculate that a complex chain of events is involved. We think that enzymatic iV-demethylation is a likely, early stage,51 followed by some form of transamination process. Oxidative Degradation — a Composite
Many microbiol genera can degrade a variety of steroidal substrates to carbon dioxide and water (T-965 and references cited therein). This degradative ability is particularly prominent among the genera which dehydrogenate A4-3-keto-steroids into the corresponding Δ1 compounds, such as Corynebacterium, Mycobac-terium, Pseudomonas, and Nocardia. As a consequence, the production of the
50
51
R. F . ,
Goutarel, R. , "Les alcaloids steroidiques des apocynacées." Hermann, Par is , 1964. Cf. Williams, R. T . , Proc. European Soc. Study Drug Toxicity 4, 9 (1964); McMahon,
J. Pharm. Sei. 55, 457 (1966).
CLASSES OF CHEMICAL REACTIONS 49
antiinflammatory 1-dehydrocorticoids by this route requires careful control to prevent loss. The paths whereby degradation occurs have been elucidated through the combined efforts of Dodson and Muir (D-171, D-172), Schubert, Böhme, and Hör hold (S-818-S-821), and Sin,. Wang, and their collaborators (Ap-79, Ap-81, Ap-83), and these paths are illustrated in the charts which follow. The first of these had to do with the degradation of the steroid nucleus.
Reduction products
Mixed products of reduction of carboxyl and carbonyl
CH3CH2-C-CH-C-C-OH
H (9)
Ap-25 0 0 II II
* - C H C H C + CH C - C - O H
Note: Stereochemistry remains the same at all centers in the degradation products as in the parent.
Dodson and Muir were the first to show that degradation followed the paths 1 - 3 - 5 or 1 - 2 - 5 , depending on the organism used. For selected Nocardia sp.
50 II. CHEMICAL CLASSIFICATIONS
it is obligatory that 9a-hydroxylation precede 1-dehydrogenation (D-172). For certain Pseudomonas sp . , on the other hand, 1-dehydrogenation must precede 9a?-hydroxyla-tion (D-171). In both instances the 9,10-seco species 5 results from the spontaneous, presumably nonenzymatic, reverse aldol reaction of postulated intermediate 4. These conclusions were confirmed later by Schubert and Sih using other organisms.
A later stage of degradation, namely, the opening of ring A, was first appreci-ated by Schubert, Böhme, and Hör hold (S-819), who isolated the degradation product having partial structure 8 from the action of Mycobacterium sp. on progesterone. This pathway was later confirmed by Sih and Wang (S-895), who used Nocardia re-strictus with androstenedione.
Sih, Wang, and their collaborators elucidated the pathway whereby 5 is trans-formed into 8 via 6 and 7. A key reaction is the 4-hydroxylation of the phenolic inter-mediate 5. Sih has recently shown that the same process is also implicated in the microbial degradation of estrone by a particular Nocardia sp. (Ap-13), which is illus-trated here. Intermediate B corresponds to 6 and C to 7. The probable structure of
Nocardia sp.
(A) (B)
HO-
HO-C
(F)
C (and 7) was deduced by the formation of the heterosteroid F (or its equivalent from 7) by reaction with ammonia. The processes which lead from C to D and from 7 to 8 have been rationalized by Sih in identical chemical terms. Compound E is pre-sumed to arise from D by further degradation. Sih and Wang and their collaborators also showed that 8 is further fragmented into 9 and thence to propionaldehyde and pyruvic acid.
(E) (D) (C)
I
CLASSES OF CHEMICAL REACTIONS 51
A second problem of great current interest has to do with the microbial degrada-tion of the side chains of cholesterol and related sterols. In 1948, Turfitt (T-1034) observed that Proactinomyces erthropolis degraded cholestenone and bile acids to a very minor degree to the corresponding etio acids. No further transformations of
C00H
C ^ H ^ C ^ ^COOH
H2
this class were disclosed until 1964, when Whitmarsh (W-1111) reported that choles-terol was degraded in poor yield by Nocardia sp. into 3-ketobisnor-4-cholenic acid, 3-ketobisnor-l,4-choladienic acid, 4-androstene-3,17-dione, and 1,4-androstadiene-3,17-dione! "
CH-COOH H C 3 ^CH-COOH
In apparently unrelated investigations, which were to assume importance later on, Dodson and Muir (D-171) showed that 19-hydroxy-4-androstene-3,17-dione was converted into estrone readily and in good yield by Pseudomonas sp. Sih and Rahim (S-894) showed that this was also true for Nocardia restrictus. Sih recognized that
52 II. CHEMICAL CLASSIFICATIONS
HOHX
estrone thus produced was singularly stable to further microbial attack, in contrast with 3-keto-A4-androstenes or 3-keto-A4-pregnenes. He reasoned that it might be possible to ferment an appropriate substrate in such a way that side-chain degrada-tion to a 17-ketone and A-ring aromatization would occur. If attack on the steroid nucleus could then be directed toward aromatization via retro-aldol loss of the angu-lar substituent at the 19-position rather than by 9a-hydroxylation and 9,10-secosteroid formation, estrone would result.
For this purpose he chose 19-hydroxy-4-cholesten-3-one, which might yield 19-hydroxy-4-androstene-3,17-dione as the sought-after intermediate of degradation. When he incubated the former with Nocardia restrictus, estrone was indeed formed in 8% yield. A culture (CSD-10), isolated from soil using cholesterol as the sole
Η·ι Πο
C*H X 2
source of carbon, gave estrone in 30% yield from the same 19-oxygenated substrate, the greatest part of the remainder being unreacted starting material. In the same way, 19-hydroxy-/3-sitost-4-en-3-one was also converted into estrone in 10% yield, thereby illustrating a desirable lack of side-chain specificity in CSD-10. In a later
H·» H?
H ,
study, Sih, Wang, and their collaborators (Ap-81) made further refinements of their method consisting principally of the replacement of 19-hydroxy-4-cholesten-3-one by 3/3,19-dihydroxy-5-cholestene 3-acetate (5) as substrate for CSD-10. Thereby estrone was produced in 72% yield. The proposed process for estrone manufacture from cho-lesterol is illustrated on the next page. Stages 1 ~5 employ methodology worked out to a high degree of perfection by a Ciba group.52 Sih has told us that the entire pro-cess, 1 ^estrone, has been carried out in his laboratory in an overall yield of 50%. Because of the brevity and efficiency of this process, one may anticipate that it or a variant will become a commercially significant method of estrone manufacture.
52Kalvoda, J . , Heusler, K., Ueberwasser, H. , Anner, G., and Wettstein, A., Helv. Chim. Acta46, 1361 (1963).
CLASSES OF CHEMICAL REACTIONS 53
π-ι Ho Ho
^ C ^ ^C"^ C
(I)
Ho H
H» Ho H2 H j
^ C ^ ^ C ^ ^ C ^ H? H^C
H,
(3) (4) (5)
CSD-lol
Estrone
In later investigations, Sih and his collaborators52a proved that cholesterol is degraded to a 17-ketosteroid by Nocardia, Mycobacterium, Corynebacterium and Arthrobacter via a sequence which involves a cholanic acid and a bisnorcholanic acid as intermediates. They also established unequivocally, using labeled substrates, the nature of the fragments to which the side chain is degraded. The pathway and label locations are illustrated.
H3 H2 H2 x
H, H^CH,
CH3CH2COOH +
C J A /COOH
C ^ / C ^ C O O H
H2 COOH
C.H -COOH
+ CH^H^COOH
5 2 aSih, C. J . , Wang, K. C. , and Tai, H. H. , J . Am. Chem. Soc. 89, 1956 (1967); Sih, C. J . , Tai, H. H. and Tsong, Y. Y., ibid., p. 1957.
54 II. CHEMICAL CLASSIFICATIONS
COOH
CH3CH2COOH
From these findings Sih has inferred the details of the mode of microbial degra-dation of the bisnorcholanic acid in the following manner. He reports that this latter sequence does not require oxygen, on which basis he presumably excludes hydroxyla-tion of the bisnorcholanic acid as an alternative path.520
COOH
-2H
C—COOH
+ H?0 tf ■COOH
aldol
He has not reached similar conclusions about the degradation of the cholanic acid to the bisnor acid. The location of the labels in the propionic acid derived from the degradation of the cholestane to the cholanic acid require that oxidative attack occur at C-26. This need not necessarily be the initiating stage of the entire degrada-tion, but if it is, the repetitive dehydrogenation52C-hydration-reverse aldol mechanism could be the means of degrading C27 to C19 steroids with the indicated microbial species. Hypotheses involving hydroxylation stages at C-24 and C-22 can be con-structed which are the equivalent of the dehydrogenation-hydration sequence, but there is no evidence for such hydroxylations.
The efficient microbial degradation of the spiroketal side chain in diosgenin and tigogenin to give l,4-androstadiene-3,16-dione (I), 16a-hydroxy-l,4-androstadien-3-one (II), and 16/3-hydroxy-l,4-androstadien-3-one (III) has been described by Ko ndo
.OH
(I) (II)
52^ A proof of his proposal is possible using H2018as the medium, thereby leading to a 17-ketosteroid labeled at the 17-carbony 1 oxygen.
52c The organisms reported here to degrade cholesterol are known to be active 1-dehydro-genation species for 3-ketosteroids.
CLASSES OF CHEMICAL REACTIONS 55
and Mitsugi (Ap-37). This degradation is effected with the representative 1-dehydro-genating species, Fusarium solani and Corynehacterium simplex. In these instances there are both parallels with and differences from the degradation of the cholesterol side chain. The pathway proposed by Kondo and Mitsugi is illustrated as follows.
y
H3C 3 I HC—
(1)
oxidation _̂_
y
H_C 3 I HC
(3)
H 3 C
1 HC
hydrolysis
J ώ
l x C / 0 H2
0 II HO-
^ 0 H2
-OH
^
- c > -
-H<
H2
-CH3
-CH3
hydrolysis
Baeyer-
Villiger
reverse nlHnl
y
H,C 3I
HC-
(2)
\
/
H,C
HC^
Λ (4)
\ y ^
II H0CH2 — C ^ c C > H - C H
OH H2 H2
0 .0>JI Η0ΗΧ.
J
f° J (5) (6)
Evidence for the intermediate stages is that the listed substrates are also transformed to (I): stage 3, kryptogenin (F. solani)) stage 5, 3/3-acetoxy-20o!-hydroxy-5-pregnen-16-one (F. solani). The parallel with the cholesterol degradation lies in the apparent requirement for an aldolase in both sequences. The structures of the end-products of degradation in the two cases appear to require different chemistry at C-20 and C-22 to rationalize their formation.
Reduction
Reduction of Carbonyl Compounds to Alcohols
Reduction of carbonyl to hydroxyl is part of the equilibrium process described in the section on oxidation of alcohols to ketones. The same mechanistic principles apply. Evidence for the correctness of the stoichiometry of the illustrated represen-tation of this reaction has been provided, using crystalline enzyme, by Hübener, Schmidt-Thome, and co-workers (H-410, N-657, S-803).
; C = 0 + NADH + H — enzyme^
H-C-OH + NAD
If it is assumed that hydride ion transfer from NADH to carbonyl is the rate-controlling step for the forward reaction, it would be expected that decreasing the electron density at the carbonyl group should increase the rate of the reduction pro-cess. Ringold and associates (R-767) have shown that cellfree extracts of Pseudo-monas testosteroni, which do not reduce the 3-carbonyl of testosterone, 2a-methyl-testosterone, or 6/3-methyltestosterone to any significant degree, do reduce testos-terones bearing fluorine at the 2a-, 4-, 6a-, or 6/3-positions, or chlorine at the 4-position to a mixture of the corresponding 3a- and 3/3-ols. Robinson, Bruce, and
56 II. CHEMICAL CLASSIFICATIONS
Oliveto (R-774) have shown that Flavobacterium dehydrogenans, which does not reduce a 17-ketosteroid unsubstituted at the 16-position, does indeed reduce 16,16-difluorode-hydroepiandrosterone and 16,16-difluoroestrone methyl ether to 17a-hydroxysteroids.
HO*
Since the presence of these highly electronegative species at positions where they may, by induction, withdraw electrons from carbonyl does have the anticipated effect, we infer support for the interpretation that hydride ion transfer is rate-controlling in this oxidation-reduction mechanism.
Sites of Reaction. Reduction of the carbonyl groups at the 3- and 17-positions by yeasts (mainly Sac char omy ces cerevisiae) were among the first microbial transforma-tions recognized by Mamoli and Vercellone (M-549, M-551, V-1046). Estradiol was synthesized conveniently from estrone (W-1085) and testosterone from androstene-dione using this method (M-543). Following the early work, many additional examples of reduction at the 3- and 17-positions have been reported, and also instances of reduc-tion at the 7-, 9-, 16-, 19-, 20-, 21-, and 22-positions.
In general, and where applicable, the use of yeast is the preferred mode of microbial reduction of carbonyl compounds, since it is unlikely to cause other trans-formations simultaneously. This specificity is equally true of protozoa, but the latter are much less convenient to use. The bacteria, fungi, and actinomycetes, in addition to their many other abilities, will often oxidize or reduce at the same site with greater facility. The direction of the change is a function of the substrate and the medium, as well as the organism.
Ordinarily the conjugated 3-carbonyl resists reduction by yeast at both the car-bonyl and unsaturated sites. An apparent exception is the case reported by Butenandt, Dannenberg, and Suranyi (B-80) of the reduction of 5a-l-androstene-3,17-dione to
CLASSES OF CHEMICAL REACTIONS 57
5a-androstane-3/3,170-diol. An instructive group of reductions at the 3-position by Saccharomyces cerevisiae was reported by Camerino, Alberti, and Vercellone (C-83).
S. cerevisiae,
HO*
ÇH3
C=0
CH, I 3
C=0
(3)
Although a major stereochemical change at the 5-position (5a in 1 vs. 5ß in 2), which alters the geometry of the A- and B-rings profoundly, does not interfere with the r e -duction at the 3-position or alter the formal stereochemistry of the resulting carbinol, the apparently minor change at the 11-position in compound 3 ( l l a -o l in 3 vs. 11-C = O in 1) leads to a carbonyl of opposite stereochemistry at the 3-position.
A more predictable approach to reduction, developed by Schubert, involves the anaerobic application of Clostridium paraputrificum to A4-3-ketosteroids (Ap-71, S-823). In all instances (testosterone, progesterone, corticosterone, cortisone) the product is the corresponding 3a-hydroxy-5ß-steroid. From A1>4-3-ketosteroids the corresponding A^a-hydroxy-öß-s te ro id is formed in good yield, with a lesser amount of fully saturated hexahydrosteroid as a by-product. From A1,4,6-3-keto-steroids or A4>6-3-ketosteroids the end-product of hydrogénation is the A6-3a-hy-droxy -5/3- steroid.
Reduction of 7-ketone to 7a-hydroxyl has been reported with Streptomyces gelaticus (H-363) and Corynebacterium sp. (T-975) among others. Reductions of this type are commonly seen with substrates in the bile acid ser ies .
In the 9,10-&Ê£Q series, 9-ketones of the type of Compound 5 (p. 49) are con-verted into 9a- and 9/3-hydroxy products by the action of Nocardia restrictus (W-1063) or Mycobacterium sp. (S-818, S-820).
58 II. CHEMICAL CLASSIFICATIONS
Several examples of simultaneous 16a- and 16/3-hydroxylation, accompanied by formation of the corresponding 16-ketone, have been reported. We described the ac-tion of Wojnowicia graminis on testosterone (H-381) leading to the aforementioned three species, and Sax and co-workers (S-793a) reported the same processes from the action of Bacillus megaterium on 4-estren-3-one. Dodson and Mizuba (D-166)
OH OH
Ύ .OH
.OH
presented an ingenious argument to the effect that 16/3-hydroxy products need not arise from 16j3-hydroxylation, but could be formed equally well from an initial 16a-hydrox-ylation of a 17-ketosteroid followed by Marker-Laws on rearrangement and reduction at the 16-position in the illustrated way. This argument cannot account for the
OH
results of Sax, since no possibility for Marker-Lawson rearrangement exists. It is not possible, however, to exclude an alternative formulation involving one oxidation and
CLASSES OF CHEMICAL REACTIONS 59
.OH
reduction stage, following 16a-hydroxylation. In any event, evidence for reduction at the 16-position remains hypothetical.
Reduction of the 17-ketone to 170-hydroxyl has been demonstrated with a wide variety of substrates and organisms. Saccharomyces cerevisiae is a very convenient and reliable reducing culture for this reaction. Reduction to 17a-hydroxyl has been reported only once in the special case of 16,16-difluoro-17-ketosteroids (R-774), dis-cussed in the mechanism section.
Reduction of 19-carbonyl to hydroxyl has been described by Sih and co-workers (S-892) from the action of Pénicillium thomii on 14/3-hydroxy-3,19-dioxo-4;20(22)-cardadienolide. This reaction was described as reversible, with the equilibrium favoring the alcohol.
Reduction of the 20-carbonyl in pregnanes of widely varied structure has been reported by many investigators. The reduction to 20/3-ol was first described by Fried, Thoma, and Klingsberg with Streptomyces lavendulae (F-284). The product of reduc-tion accumulated in the mycelium, whereas the products of oxidation remained in the
CH3 I 3
C=0
CH, I 3
HO-C-H
broth. For synthetic purposes, the preferred organisms for this reduction are Streptomyces hydrogenans (L-522) and other Streptomyces sp. (C-110), which afford the desired process, uncomplicated by major competing reactions. Hiibener and col-laborators (H-410, N-657, S-803) isolated an inducible, crystalline 200-hydrogenase from S. hydrogenans, which they demonstrated could be used to catalyze reduction or oxidation at the 20-position with a wide variety of substrates.
60 Π. CHEMICAL CLASSIFICATIONS
Reduction of 20-ketopregnanes to 20a-hydroxyl compounds, by a microbial pro-cess free from unrelated coincident reactions, was first reported in our laboratory with the use of Rhodotorula longissima (C-110). The application of this organism to a
broader selection of 20-ketopregnanes was described subsequently by Idler and co-workers (C-122, I-413a). No examples of this reduction have been reported with fungi, actinomycetes, or bacteria. Thus far, yeasts (C-88), algae (L-527), alfalfa seedlings (L-526), and many mammalian species have been shown to give reduction products with this stereochemistry.
Reduction of 22-aldehydes to the respective carbinols was first described by Murray, Peterson, and their collaborators (M-578) with Rhizopus nigricans and Rhizopus arrhizus, concomitant with hydroxylation at the 11a- and 6/3-positions. Pénicillium lilacinum (E-202) and Gliocladium catenulatum (W-1068) have been re -ported to give reduction at the 22-position, free of major side reaction. Ambiguity in the descriptions of the starting materials in these reactions make it uncertain as to whether the reductions occur principally with'retention of configuration at the 20-position or with inversion. It is clear, however, thatG. catenulatum leads to an equilibration of the starting material at the 20-position, at least in part.
Reduction of Carbon-Carbon Double Bonds
This type of reaction may be divided into two categories: (1) reduction of iso-lated double bonds and (2) reduction of conjugated double bonds. There are very few examples of the former in the steroid field, all involving the use of unidentified fecal anaerobes to reduce Δ5-compounds to the 5/3-series (C-133, S-914), and there is no adequate basis for the presentation of arguments about mechanism.53
The reduction of double bonds conjugated with keto groups may be viewed as part of the illustrated equilibrium process, the reverse of which is the dehydrogena-tion of ketosteroids. The nature of the reagent X, be it protein-bound flavin, quinone,
XH,
or another oxidizing agent, has been discussed in the section on dehydrogenation. If this view is accepted, then the stereochemical restrictions developed for dehydrogena-tion should apply.530 These restrictions are that the leaving (or entering) hydrogens at the 1- and 2-positions are axial and trans (ley,2/3). The evidence for the equilibrium
53 The conversion of cholic acid into 7-deoxy bile acids by mixed intestinal microorganisms is considered to proceed via elimination of the 7a-hydroxyl group followed by reduction. These reductions have not been demonstrated with pure cultures. Bergstrom, S. , Danielsson, H. , and Samuelson, B. , in MLipid Metabolism" (K. Bloch, ed.) , p. 316. Wiley, New York, 1960.
530 Whether these may be generalized from the studies with one organism, B. sphaericus, remains to be established.
CLASSES OF CHEMICAL REACTIONS 61
nature of the reaction comes from Goodman, May, and Smith (G-296) who showed that C. simplex and B. cyclo-oxydans interconvert triamcinolone and 1,2-dihydrotriam-cinolone.
C. simplex or B. cyclo-oxydans
Sites of Reaction. Reduction of conjugated double bonds was first observed by (M-548) with a crude culture of putrefactive bacteria. The pure
reduced 3-keto-A4-androstenes to 3-keto-This culture is no longer
Mamoli and Schramm culture, described as Bacillus putrificus, 5ß-androstanes and 3a-hydroxy-5/3-androstanes (M-545). available (E-202), but a modern equivalent is Clostridium paraputrificum, described by Schubert (Ap-71, S-823). The properties of the latter are described in greater detail in the section on reduction of carbonyl groups.
Butenandt, Dannenberg, and Suranyi (B-80) reported the reduction of A ^ - k e t o -5a-steroids to 3/3-hydroxysteroids with yeast.
S. cerevisiae
HO Λ ^ ,
Reductions of 3-keto-Δ4-substrates with fungi or actinomycetes may lead to either 4,5a- or 4,5/3-dihydro products, but these reactions are usually incidental to hydroxylation elsewhere in the substrates (E-201, P-718, P-725, P-729). Selective reduction of A1?4-3-ketosteroids to Δλ-5β-steroids with Streptomyces sp. has also been described (G-314).
Sfreplomyces sp.
There is indirect evidence for the reduction of 12a-hydroxy-3-keto-4,6-chol-adienic acid at Δ6. Hayakawa and collaborators (H-358, H-367, T-974) have shown that cholic acid is transformed into the illustrated products (1-5) by Corynebacterium simplex and other Corynebacterium sp.
If one places the products in the sequence shown here, the elimination of the 7a-hydroxyl group in 2 need not necessarily be enzyme-catalyzed. Conversion of 3 into 4 follows logically and requires enzyme mediation. Other routes to the formation of the same products are not excluded.
The reduction of 16-dehydroprogesterone, accompanied by 11 «-hydroxylation, from the action of Rhizopus nigricans (M-579, M-601, M-605) or Aspergillus niger
62 II. CHEMICAL CLASSIFICATIONS
HO*
COOH Corynebacterium sp.
COOH
(2) (3)
COOH
(4) (5)
(M-603) affords lla-hydroxy-17û!-4-pregnene-3,20-dione. The thermodynamically more stable configuration of the side chain in pregnenolone and 3/3-hydroxy-5a-pregnan-20-one is the /3-form.54 If one makes the reasonable assumption that this
0 '
is also true for lla-hydroxyprogesterone vs. its 17o?-epimer, it becomes possible to develop a speculative argument about the stereochemistry of the attachment of the steroid to the enzyme. If one chooses to argue that reaction is complete at the enzyme surface by 1,2-addition in the illustrated sense, then the hydrogen at the 17-position must have been delivered from the /3-side, and the product thus produced must be free to alter the angle of attachment at the 17-position from the initial plana-rity of the starting material to the quasi-axial of the product without steric inter-ference from the enzyme. This may be accommodated if the steroid is attached to the enzyme by its ß-face.
Butenandt, A. , and Fleischer, G., Ber. 70, 96 (1937); Butenandt, A. , and Mamoli, L. , ibid., £3, 1847 (1935). —
CLASSES OF CHEMICAL REACTIONS 63
CH3
I c=o
An alternative treatment of the problem is to assume the reversal of the Ringold mechanism for dehydrogenation (as developed for A-ring transformations) to account for the observed reaction. In specific terms this involves enzyme-mediated attack by hydride ion on the 16-position as the initiating stage. The mechanism requires the formation of the illustrated enol as the intermediate. The enol must then be protonated
CH, I 3
c=o
[H]"
enzyme
CH3
C -0~
H +
CH3
C=0
and go back to the ketone before it leaves the enzyme surface in order to attain the thermodynamically less favorable 17o?-stereochemistry. This treatment again implies attachment of the substrate and the transition state derived from it to the enzyme by the /3-face. The Ringold mechanism has the apparent merit of requiring no change in geometry at the 17-position during the enzyme-mediated, hydride ion transfer stage. Protonation of the enol would be spontaneous, and it would be necessary to invoke only a steric but not a catalytic role for the enzyme during this part of the process.
Reduction of Steroidal Bromide
Laskin and Diassi (L-492) have reported the only example of reduction of a ste-roidal bromide. Cylindrocarpon radicicola transformed 9a-bromo-ll-ketoprogester-one into 1-dehydro-ll-ketotestololactone. Reductive removal of halide from an a-halo -ketone is well known in organic chemistry and can be done very efficiently with a vari-ety of reducing systems.
Esterification and Hydrolysis
Hydrolysis of Esters to Give Steroid Alcohols
The mechanism of catalysis for hydrolysis of steroid esters to steroid alcohols has not been elucidated in particular. In view of the nonspecific nature of esterases, however, it might be possible to carry over mechanistic conclusions from the studies with simpler esters . A favored formulation of this process by Bender and Kezdy55 is
'Bender, M. L. , and Kezdy, F. J. , Ann. Rev. Biochem. 34, 49 (1965).
64 II. CHEMICAL CLASSIFICATIONS
shown here. The enzyme provides the required imidazole and hydroxyl groups. Water may participate in the cleavage of the steroid ester and is involved in the regeneration of the enzyme hydroxyl site.
enzyme
H NI l \ C—OR
N1
enzyme
f*l ° Ν χ
ΊΗ ^R
0
enzyme
enzyme
R = steroid
1 1 , -l\L 0 ^ .OR
Ή CC I R 0
H
JO ί \ i J
Hydrolysis of steroidal 21-acetates was among the earliest transformations recognized. Mamoli (M-541) found that Cor ynebac ter turn mediolanum could be used to transform 21-acetoxypregnenolone into deoxycorticosterone. Since then it has been shown that nonspecific esterases are common among bacteria, fungi, and actino-mycetes.
Acetylation is employed widely as a protective device for hydroxyl groups during the chemical manipulation of steroids. Successful use in this way implies the ability to remove the protective group following completion of the synthetic pro-gram. We have found that Flavobacterium dehydrogenans (A-16) contains what we believe to be a "universal" system of deacetylase(s). The acetates which we have hydrolyzed with its aid include Iß- (N-689), 30- (N-689),56 11a- (unpublished), 11/3-(C-129), 15a- (unpublished), 16a- (S-839), 16/3- (S-839), 17a- (N-690), 17/3- (G-304), 20/3- (unpublished), and 21- (C-129).56 The yields are usually very high, and major coincident reactions, namely, oxidation of 3-hydroxyl to ketone and isomerization of Δ5 to Δ4, are often useful.
While microbial hydrolysis of esters other than acetates might be expected to be equally common, relatively little reliable documentation of these reactions exists in the steroid field. The reason for this is clearly that acetates are the preferred esters
See also South African Patent 3462 (1955).
CLASSES OF CHEMICAL REACTIONS 65
for most synthetic purposes, and consequently other esters have been subjected only rarely to study in microbial transformations. Among the few examples are the hydrolyses of tes tololac tone to testolic acid by Pénicillium lilacinum (P-737), other Pénicillium sp. (H-398), Cephalosporium acremonium (H-398), and Aspergillus flavipes (H-398).
A convenient source of esterase for "in vitro" laboratory use is malt enzyme (diastase, J . P . ) the application of which was described by Noguchi (N-672, N-673). Noguchi reported the successful hydrolysis of acetates at the 16a-, 170-, 20a-, 20/3-, and 21-positions (N-672). He also extended this method to 21-esters of other straight-chain aliphatic carboxylic acids (formate, butyrate, and caprylate), dibasic aliphatic hemiesters (hemisuccinate and hemitartrate) and AT-substituted amino acid esters (dimethylaminoacetate and diethylaminoacetate) (N-673). 17/3-Formate was hydro-lyzed, but 17ß-propionate was not.
Esterification of Steroid Alcohols
Only two reports of examples of this reaction class have been made. McGuire, Maxwell, and Tomkins (M-572) described the action of Saccharomyces fragilis on androstenedione, which afforded testerone acetate. The product arose from sequential
reduction followed by acetylation. Holmlund and collaborators (H-404) observed the acetylation of the 16,17-acetonide of 9a-fluoro-16ai-hydroxyhydrocortisone by
ChLOH
Trichoderma glauca. These examples are principally of academic interest as further evidence of the reversibility of enzymatic reactions. The mechanism which operates here is possibly the reverse of that illustrated for hydrolysis.
N-Acetate Formation from Amines
The only example of this reaction class was described by Smith and co-workers (S-911) from the action of Streptomyces roseochromogenus on 21-amino-9a-fluoro-ll/3, 17a-dihydroxy-l,4-pregnadiene-3,20-dione to give the 21-N-acetate.
ΗΟ^
I 2 2
C=0
WoH S. roseochromogenus
-CH,
66 II. CHEMICAL CLASSIFICATIONS
The mechanism of acylation may be related to that of esterification of hydroxyl groups.
Hydrolysis of Oxides to Alcohols
The simple hydrolysis of oxides with Saccharomyces cerevisiae, first described by Camerino and Sciaky (C-87), leads to glycols with diaxial opening. This reaction is then the mechanistic equivalent of a normal, acid-catalyzed opening of an oxide,
C H , I 3
C=0
CH, I 3
c=o
c=o
with water acting as the nucleophile. One may speculate that the enzyme is acting as a reversible proton donor-proton acceptor species, perhaps involving an imidazole as the combined proton source-proton sink. The stereochemical problems attendant to the formation of a cyclic 9-member ring transition state might be mitigated by con-sidering that the participating water need not be a single molecule, but may be a hy-drogen-bonded agglomerate.
H ^
0 I 0 - H H
H
enzyme enzyme
A special case of oxide opening involving Wagner-Meerwein rearrangement was described by Camerino and Vercellone (C-88). This is analogous to a nonenzymatic, acid-catalyzed process studied by Heusler and Wettstein57 and in our laboratory.58
57Heusler, K., and Wettstein, A. , Ber. 87, 1301 (1954). 58Shapiro, E. S., Steinberg, M. , Gould, D. , Gentles, M. J. , Herzog, H. L. , Gilmore,
M., Charney, W. , Hershberg, E. B . , and Mandell, L . , J . Am. Chem. Soc. 81, 6483 (1959) (and preceding papers in the series).
CLASSES OF CHEMICAL REACTIONS 67
C-CH3 •••OH
;H3?V
The initiating stage here appears to be identical with the normal oxide opening. Molecular geometry then favors intramolecular methyl migration (13 -17) over nucleo-philic, intermolecular hydration at the 17-position. The reaction is completed by proton loss from the 14-position.
Hydrolysis of Glycosides
Cleavage of glucose from selected steroidal glycosides by fungi was recognized and studied by Stoll, Renz, and Brack (S-936a). Ability to perform this transforma-tion is especially prominent among Aspergillus and Pénicillium sp. It is not clear from the available evidence whether the reaction in question is hydrolysis or a t rans-glycosylation. The generic form of the reaction, which embodies this uncertainty, can be given as follows:
R-O-R1 4- R-0H -R ' -O -R" + R-OH
R = steroid portion of glycoside R'= sugar portion of glycoside R"= sugar moiety or hydrogen
The substantial literature on transglycosylation has been reviewed by Stodola.59
The Stoll group observed the selective cleavage of glucose from several cardio-active glycosides. In each case (scilliroside, digilanide A, and deacetyldigilanide A) glucose was an end group, the cleavage leading thereby to a partially degraded glyco-side. Such a result is difficult to obtain by other than enzymatic techniques. Later work by Krider, Cordon, and Wall (K-478), using the same fungal genera, showed that this technique could be applied to steroidal saponins to give sapogenins.
Isomerization of Double Bonds Isomerization of the double bond from Δ5 to Δ4 was among the reactions first
recognized by Mamoli. With Corynebacterium mediolanum he converted 3/3,21-dihy-droxy-5-pregnen-20-one 21-acetate into deoxycorticosterone (M-541). From our
experience Flavobacterium dehydrogenans can be used very efficiently in the same way (N-688, N-689). In general, enzymes which promote the isomerization reaction are
Stodola, F. , "Chemical Transformations by Microorganisms," p. 65. Wiley, New York, 1958.
68 II. CHEMICAL CLASSIFICATIONS
widely distributed among oxidizing microorganisms. We know of only one oxidizing organism, Actinoplanes mis s our tens is (Ap-45), which does not also sequentially iso-merize Δ5 to Δ4.60
The mechanism of the enzyme-catalyzed isomerization has been studied in de-tail by Talalay and Ringold. Talalay, Wang, and Kawahara isolated and crystallized the induced isomerase from Pseudomonas testosteroni (K-437, T-972)61 and showed that its use required no cofactor. From study of the isomerization in deuterium oxide, they demonstrated no deuterium incorporation into the steroid and inferred that the isomerization involved a transfer of hydrogen from C-4 to C-6. Malhotra and Ringold proved that hydrogen is transferred from the 4/3- to the 6/3-position by using appropriate, deuterium-labeled substrates (Ap-44). They also established that the transfer is intramolecular. The present view of the mechanism which repre-sents a synthesis of the Talalay and Ringold findings is illustrated here.62 This for-mulation requires 8-member ring (1) and 10-membered ring (2) transition states
which Talalay has asserted are shown to be accommodated easily, in appropriate scale models.62 Talalay has inferred the histidine catalysis from enzyme inactiva-tion studies with méthylène blue. Some evidence for probable reversibility comes from the work of Ward and Engel63 with sheep adrenal enzymes. They showed that 4-androstene-3,17-dione could be transformed into dehydroepiandosterone. The first
stage of this reaction is presumed to be the deconjugation of Δ4 to Δ 5 . It has also been reported that Bacillus pulvifaciens converts 6/3-hydroxy-4-androstene-3,17-dione into 5a-androstane-3,6,17-trione (1-420), which may be accounted for by the action of an isomerase.
6 While Flavobacterium dehydrogenans isomerizes the double bond smoothly in a 3/3 -hydroxy^ 5 -subst ra te , presumably after oxidation at the 3-position, it does not isomerize the double bond in a 3 - k e t o ^ 1 , s -substrate (N-690).
61 Kawahara, F. S., Wang, S. F. , and Talalay, P. , J . Biol. Chem. 237, 1500 (1962); Wang, S. F . , Kawahara, F . S., and Talalay, P. ibid., 23§, 567 (1963).
62Talalay, P . , Ann. Rev. Biochem. 34, 352 (1965). 63Ward, M. G. , and Engel, L. L. , J. Biol. Chem. 239, PC3604 (1964).
CLASSES OF CHEMICAL REACTIONS 69
The isomerase from Ps. testosteronih&s also transformed A5(10)-3-ketosteroids into their Δ4-counterparts in vitro (T-972). The appropriate substrates have not been investigated with intact cultures, but there is no reason to doubt than an equivalent r e -action would take place in vivo.
Miscellaneous Addition, Rearrangement, and Elimination Processes The following reaction classes have been identified in the presence of microbial
systems. The necessity for enzymatic catalysis is not proved in many of these cases and is specifically excluded in two.
a. Wagner-Meerwein rearrangement b. Decarboxylation c. Aldol and reverse aldol reactions d. Michael addition e. D- Ho mo annulatio n f. Enolization of carbonyl compounds g. Dehydration h. Amination
Wagner-Meerwein Rearrangement
Saccharomyces cerevisiae was used by Camerino and Vercellone (C-88) to trans-form 16o?,17û!-oxido-20-ketopregnanes. The products thus produced are those which have also resulted from acid-catalyzed, hydrolytic attack on the oxide64 followed by
reduction at the 20-position. The Wagner-Meerwein rearrangement of the angular methyl group from the 13- to the 17-position is presumably not under enzymatic con-trol per se, but follows as a consequence of the enzyme-catalyzed opening of the oxide, a reaction which has been demonstrated in other cases (cf. p. 66) with yeasts.
Decarboxylation
Decarboxylation of a 0-ketolactone has been shown by Urech, Vischer, and Wett-stein (U-1044) in the illustrated case. The reaction also proceeded in the medium alone, in the absence of Fusarium solani or enzymes from it, when the appropriate 17-keto-(18 — 11) lactone was used as substrate.
Heusler, K. , and Wettstein, A. , Ber. 87, 1301 (1954).
70 II. CHEMICAL CLASSIFICATIONS
Reverse Aldol Reaction
Dodson and Muir showed that the reverse aldol reaction is a key step in the degra-dation of the B-ring (D-171, D-172). In the illustration, 9a-hydroxylation of a Δ1?4-3-ketosteroid with Pseudomonas sp. affords an intermediate which then experiences clea-vage between the 9- and 10-positions. The same investigators also reported another
variant of the same reaction, in which formaldehyde is lost from 19-hydroxy-l,4-andro-stadiene-3,17-dione, which was produced in situ by the A^dehydrogenation of 19-hy-droxy-4-androstene-3,17-dione. The latter sequence represents a key transition in the conversion of cholesterol into estrone as described by Sih.
Pseudomonas s p. HOHX
There is no evidence that an enzyme is required for the reverse aldol stage of either of the illustrated reactions. It is likely that an aldolase is required for the reverse aldol reactions described in the section on degradation of the cholesterol and diosgenin side chains (Ap-37; Sih and collaborators52a).
Michael Addition
Intramolecular Michael addition of an 11/3-hydroxyl group to a 3-keto-Δ1-system has been reported by Gnoj and associates (G-292). There is no reason to believe that an enzyme is required for the addition, which follows enzymatic deacetylation at the 11-position.
CI-LOH I 2
CLASSES OF CHEMICAL REACTIONS 71
D- Horn oannulation
D-Homoannulation was among the first transformations described by Fried and his collaborators (F-283) using Aspergillus niger with 17a-hydroxyprogesterone.
Later work by Goodman and Smith (G-297) with triamcinolone and related 16ai-hy-droxycorticoids established that, for the examples studied, D-ho mo annulation is non-enzymatic, the reaction being promoted by ferrous or ferric ion in the presence of
Λ
CHoOH I C-O X-OH
•OH ^
CHoOH
• OH 0
OH
calcium carbonate and inhibited by phosphate ion. Whether this mechanism also applies to the reaction of ΙΊα-hydroxyprogesterone is open to some question, since 17a-hydroxy-20-ketosteroids D-homoannulate much less readily than do 16a-hydroxy-corticoids.
Enolization of Carbonyl Compounds — Inversion at the a-Carbon
From deuterium exchange experiments with 3-ketosteroids, it has been inferred that enolization is a common, microbially induced process. The same conclusion is also supported by the observed isomerization at 20- of 22-aldehydes. Wechter (W-1068) has described the inversion of 3-ketobisnor-4-cholen-22-al to the 20-iso compound by Gliocladium catenulatum, for which a reasonable mechanism is the illustrated enoliza-tion.
Dehydrative elimination of hydroxyl groups is well known from the enzymatic conversion of saturated to mo nouns aturated fatty acids.65 Incubation of cholic acid with rat feces under anaerobic conditions gives a mixture of 7-deoxy products, which were presumed to have arisen through dehydration of the la -hydroxyl group, followed
1962. 65Hayano, M. , in MOxygenasesM (O. Hayaishi, ed.), p. 229. Academic Press, New York,
Dehydration
72 II. CHEMICAL CLASSIFICATIONS
by reduction of the resulting Δ6 double bond.66 A related process has been seen by Hayakawa and his collaborators from the action of Corynebacterium simplex (H-358, H-367, T-974) and Streptomyces rubescens (H-362) on cholic acid. One may infer
CH2
CH2 I 2
C-0H 0 £ simplex^
0' ^ ^ 0 "
(2) (3)
that the antecedent of the three illustrated products is 7 a, 12a-dihydroxy-3-keto-4-cholenic acid [actually isolated from the reaction (H-365, H-367)], which then suffers dehydrative elimination to give the Δ4>6 -diene (1), followed by reduction to the 3-keto-Δ4 (2), and finally dehydrogenation to the Δ1*4 -diene (3).
Whether the elimination at the 7-position is enzyme-catalyzed or merely a purely chemical reverse Michael reaction has not been established.
Dehydration of the 50-hydroxyl group in cardiac aglycones has been reported by Nozaki (N-679) with Absidia orchidis and by Sih and associates (S-891) with Chaeto-mium globosum. In each case elimination presumably followed oxidation of the 3/3-hydroxyl to ketone and may be nonenzymatic.
Amination The only example of amination in the steroid field has been reported by Smith
and collaborators (S-911). Streptomyces roseochromogenus on 9a-fluoroprednisolone afforded the 21-deoxy-21-acetylamino product. This reaction may be following the illustrated path.
S. roseochromogenus
••OH
0 II C-H | c=o | > ^ 0 H
CH2—NH2
C=0
|ΑθΗ
1 1
R 1
CH=N-C-C00H C=0 H 1
K
\y
> \ 0 H
' '
Γ ? Ί CH2—N=C—COOH
ç=o
K
r"
^Λ-ΟΗ
1 66Bergstrom, S., Danielsson, H. , and Samuelsson, B . , in "Lipide Metabolism" (K.
Bloch, ed.) , p. 305. Wiley, New York, 1960.
CLASSES OF CHEMICAL REACTIONS 73
Resolution of Steroids from Total Synthesis Total synthesis has become an important factor in the commercial production
of steroids. Velluz and collaborators at Roussel have devised a practical method for the manufacture of 19-nor steroids and estrogens.67 Implicit in any total synthesis is the requirement for either a resolution or a stage of asymmetric reaction. Both methods have been used successfully to provide steroids of natural configuration. Of the two techniques the latter is to be preferred, since it is capable of converting all the substrate into useful product, whereas the former can only provide half of the pro-duct in natural configuration.
Gibian and collaborators (Ap-24) succeeded in devising an efficient asymmetric microbiological stage as part of a synthesis of estradiol methyl ether. The optically
CH,0
Saccharornyces sp.
CH.0
(I) (2)
inactive diketone 1 was reduced to the optically active, natural series (d) ketol 2 with the aid of Saccharornyces pastorianus, S. carlsbergensis, or, best of all, S. uvarum. Bacillus thuringiensis, on the other hand, afforded exclusively the epimer at the 13-position.
The first successful use of a microbial stage to separate a racemic mixture was described by Vischer, Schmidlin, and Wettstein (V-1055) who prepared natural {d)~ aldosterone by 21-hydroxylation of a <i,Z-precursor with Ophiobolus herpotrichus.
d,L-
CHoOH HO I
I C=0
/ - starting material
The natural series of steroids is not necessarily the preferred substrate for all microorganisms. Greenspan and collaborators (Ap-28) have described oxidation of 17/3-hydroxysteroids with Flavobacterium dehydrogenans and A1-dehydrogenations with Corynebacterium hoagii, which resulted in the transformation of both d and I substrates.
Chem. Eng. News 42, 42 (1964).
CHAPTER I I I
THE CONSTRUCTION AND USE OF TABLE I
ORDER OF THE TABLE
The entries in Table I are all products of microbial transformation. With few exceptions, compounds are recorded in this table only when a detailed procedure has been given in the cited reference. Specifically excluded are the lists of transforma-tion products, given without experimental detail, which occur often in the patent liter-ature. As a general rule, one is better advised to use the scientific literature, as distinct from the patent literature, as the prime guide.
The table entries are recorded in an order determined by the following rules, which are applied sequentially :
(a) According to increasing carbon content (b) According to increasing hydrogen content (c) According to increasing oxygen content (d) According to the alphabetic placement of hetero atoms, e .g. , Br, Cl,
F, I, N, S; for compounds of identical C, H, and O content; BrCl (as in C21H2803BrCl) precedes Br2 (as in C21H2803Br2 ); FS precedes N (e.g., C21H2803FS precedes C21H2803N)
Products of known empirical formula, but unknown structure, are shown at the end of each group of entries having common empirical formulas. Systematic organic chemical nomenclature has been used, except for sapogenins and steroidal alkaloids. Common names of the principal hormones are given parenthetically.
Where an isotope (other than the most common) of a given element is present, the empirical formula is constructed without special reference to the label (e.g., C21H29H303 is given under C21H30O3 ). The label is indicated by the use of a suffix symbol in the product name (e.g., 21-hydroxy-4-pregnene-3,20-dione 21-018).
NOMENCLATURE
The following systematic stem names were used for the indicated structures.
C21 I
Estrane Androstane Pregnane
74
NOMENCLATURE 75
I2' /C=0 r ç/ 23
C H > 0 22
Cardanolide Bufanolide
C I X^ X^ /C
23 ^ C 2 7
C ho la nie acid Cholestane
Stigmastane
The problem of the nomenclature of the few sapogenin and steroidal alkaloid entries was evaded by the use of common stem names. These are defined elsewhere.68
Configuration of any substituent attached to a ring carbon of the steroid nucleus is defined as ß when that substituent projects above the plane of the steroid nucleus and as a when the substituent projects below the plane. Substituents which have the 0-configuration are shown attached to the nucleus by solid lines, and those which have the «-configuration, by dotted lines. Configuration of hydrogen at the 5-position is always defined by 5a- or 5/3- preceding the stem. Configurations at the 8-, 10-, 13-, and 17-positions are*understood to be ß unless otherwise indicated, and configurations at the 9- and 14-positions are understood to be CÜ. Configuration at the 20-position is specified as a or ß following the Fieser convention.68
No more than one class of suffix designation for substituents is affixed to any stem. All remaining substituents are expressed in prefixes, arranged alphabetically. The alphabetical arrangement of prefixes depends only on the root term for the pre-fix and is independent of the number of substituents of the particular type. For ex-ample, fluoro precedes hydroxy, fluoro precedes dihydroxy, hydroxy precedes methyl, and trihydroxy precedes methyl.
68 Fieser, L. F . , and Fieser, M., "Steroids." Reinhold, New York, 1959.
76 III. CONSTRUCTION AND USE OF TABLE I
The prefix nor defines a steroid with cne less carbon atom than the stem indi-cates (bisnor - two carbon atoms less, etc. ). Where no number or letter precedes nor, the carbon which has been dropped is the highest-numbered stem member. In other instances, the carbon atom which is missing is shown by the number or letter preceding nor (e.g., 19-nor-4-pregnene-3,20-dione or A-nor-3-androstene-2-one). Where the letter designation is used, ring contraction of the indicated ring is present, and the highest numbered carbon atom in that ring is absent.
The prefix homo defines a steroid with one more atom than the stem indicates. The rules for definition of the locus of the change follow those for norsteroids. The homo atom, which is usually a ring member in the compounds treated here, is given a number designation of the highest-numbered atom of the given ring, followed by the letter a.
I7a
D [ D- homo- i7a-oxa 16
15
Oxa, aza, and thia designate the replacement of an actual or hypothetical carbon by oxygen, nitrogen, and sulfur, respectively.
Seco defines a bond normally present in the steroid skeleton, which is broken in the case in question.
9,10-seco-
Retro defines a steroid with the 9/3,10a-configuration (in place of the normal 9a, 10/3).
Entries of the same empirical formula are placed in alphabetical sequence ac-cording to the name defined by the stem plus the suffix: androstadiene, androstane, androstene, pregnadiene, pregnane, and pregnene.
For compounds with identical stem names, ranking is determined by the alpha-betical position of the prefix: bromo, ethyl, fluoro, hydroxy, methyl, etc. Where there is more than one prefix, that which begins with the letter closest to a deter-mines the rank of the compound. Designations such as di and t r i are ignored for this purpose, e .g. , dihydroxy is an h prefix, not a d prefix. For compounds with identical prefixes and stem names, the order is determined by the position of the lowest-num-bered substitutent, e .g . , l a -hydroxy- 4-pregnene- 3,20-dio ne precedes 6/3-hydroxy-4-pregnene-3,20-dione. For identically positioned substituents ot always precedes ß.
DESCRIPTION OF THE TRANSFORMATION LEADING TO THE PRODUCT
A shorthand notation is used to show the transformation(s) which led to the illus-trated product. Symbols are defined as follows.
DESCRIPTION OF THE TRANSFORMATION LEADING TO THE PRODUCT 77
,x>y
,x(y)
Δ (y-a)
x-OH
x-OH- x - C = 0
x -C=0 ^ x - O H
ΔΧ - y ß - H
enol. o r enoliz .
ketoniz.
degradat ion [X,Y] (substra te)
Me
Inser t ion of a double bond between the numbered carbon (x=l, 2, 3, e tc . ) and that of next higher number
Inser t ion of two double bonds, x defining the un-sa tura t ion of the lower number and y the unsa tu r -ation of the higher number (according to the p r e -ceding rule)
Inser t ion of a double bond between the indicated, nonconsecutively numbered carbon a toms
Inser t ion of a double bond into a p r e c u r s o r with hydrogen or another subst i tuent in the i l lus t ra ted configuration, e . g . , Δ4(5/3-Η) means double bond introduction into a 5/3-steroid at Δ4
Hydroxylation at the indicated s i te
The i l lus t ra ted functional group is t r ans fo rmed in the indicated way
The indicated hydroxyl group is oxidized to ketone
The indicated ketone is reduced to hydroxyl
The indicated double bond is reduced and hydrogen en te r s in the noted configuration, e . g . , Δ4 ·-5/3-H means that the Δ4 double bond has been r e -duced, with the hydrogen at the 5-posit ion entering ß -Enolization of a carbonyl group Revers ion of an enol to the corresponding ketone
The degradat ion of the indicated r ings [X,Y] of the i l lus t ra ted subs t r a t e has o c c u r r e d . The chem-ical changes he re a r e so numerous and, in some c a s e s , incompletely unders tood that individual s t eps a r e not shown
CH,
Fo
O II
H - C -
Ac
O
CH3C-
O
P r
Bu
i-Bu
CH 3 -CH 2 -C-O II
CH3-CH2-CH2-C-O
(CH 3 ) 2 -CH-C-
78 ΙΠ. CONSTRUCTION AND USE OF TABLE I
rev. aldol or reverse aldol
o l i
HCH
YIELD
Where a yield is reported by the investigators, it is recorded in the table. The term (cr. ) following yield means that the figure applies to a product which in our judgment is significantly less pure than the analytical sample of the indicated com-pound. Where no yield has been reported, the yield column shows a dash (-). Where the yield is less than 1%, it has sometimes been given as " trace" (tr. ).
ORGANISM
The organism is described in the language of the particular reference, with few exceptions {Corynebacterium is used in preference to Arthrobacter, and Streptomyces in place of Actinomyces). When an organism has been unidentified in early work, but characterized in later reports, the final assignment is used. For a more exact des-cription of the organism (source or culture number), it is necessary to consult Table III "Transformation by Genus. " Where the author has catalogued a list of identical transformations, using different species from the same genus, we have sometimes abbreviated his report as a single entry with a generic description (e.g. , Aspergillus sp. for a list of Aspergilli which all 1 la-hydroxylate Compound S ). These cultures are listed individually in Table III "Transformation by Genus" and are marked with an asterisk in that table.
Transformations with mixed cultures have been omitted from this table except in a few cases of historical interest.
In general, reactions with cellfree enzymes and enzyme systems, which have not also been reported for the intact culture, have not been included in this table.
CONSTANTS
Melting points are given to the nearest degree (centigrade), excepting those values which have been reported by the investigators to the half degree (e.g., 244. 5-246). Rotations are rounded off to the nearest degree, with the same exception. The rotation solvent is given in brackets after the reading: a, acetone; c, chloroform; d, dioxane; e, ethanol; m, methanol; and p, pyridine.
In several instances a rotatory dispersion curve has been reported by the in-vestigator with no sodium D line read-out. An asterisk has been entered in the rota-tion column in these cases. No temperatures have been recorded for rotations on account of the lack of space in the table and the relative insensitivity of rotations to minor temperature changes. Almost all rotations were reported at 25 ± 5°C.
REFERENCES 79
REFERENCES
The reference for each entry is given by coded citation in the reference column. These citations are arranged alphabetically in the Bibliography. None of these refer-ences are listed in the Bibliographical Appendix. The references are drawn from the scientific literature and the United States Patent literature through January 1964, with a few subsequent inclusions.
Many later references to the scientific literature (not patent literature) through December 1966 are in the Bibliographical Appendix. These are annotated briefly in most cases and have been used, where pertinent, in the discussion sections but not in the tabular sections of this book.
80
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C 1 3 H 1 8 ° 3
C 1 3 H 1 8 0 4
^13^20^3
C 15 H 22°4
C 1 5 H 2 4 ° 3
C1 8H1 903Br
C 1 8 H 1 9 ° 3 F
^1 8^20^2
^18"20^3
C1 8H2 102F
^18"22θ2
NAME OF REACTION PRODUCT
3 a a - H - 4 a - [ 3 ' -propionic ac id]-5a -hydroxy - 7a/3 - methyl -hexahydro -1 -indanone lactone
3aa-H-4a-[3* -propionic acid]-5/3-hydr oxy -7a/3- methyl -hexahydro-1 -indanone lactone
3aa-H-4a- [3 f -propionic acid]-7a/3 -methylhexahydro - 1 , 5 -indanedione
3aa-H-4a- [3 f -n -propanol ] -7a/3 - methy lhexahydr o - 1 , 5 -indanedione
l /3-acetyl-3aa-H-4a-[3» -propionic acid]-7a/3-methyl-hexahydr o - 5 - indanone
l /3-acetyl -3aa-H-4a-[3 f -n-pr opanol] - 7aß - methy lhexa -hydro - 5 - indanone
9 a - b r o m o - 3 - h y d r o x y - 1 , 3 , 5 ( l O ) - e s t r a t r i e n e - l l , 17-dione
6a - f luo r0 -3 -hydroxy-1 ,3 ,5 ( l O ) - e s t r a t r i e n e - l l , 17-dione
3 - h y d r o x y - l , 3 , 5 ( 1 0 ) , 6 -es t r a te t r aene -17 -one
3-hydroxy-1 ,3 ,5(10) , 7 - e s t r a -te t raene-17-one (equilin)
3-hydroxy-14/3-l ,3,5(10),9 ( l l ) - e s t r a t e t r a e n e - 1 7 - o n e
3 -hyd roxy -9ß , l l / 3 -ox ido - l , 3 , 5(10)-es t ra t r ien-17-one
6 a - f l u o r o - 3 - h y d r o x y - l , 3 , 5 (10) -es t ra t r ien-17-one
3 -hydroxy- l , 3 ,5 (10 ) -es t r a t r i en -16-one
TRANSFORMATION
degradation [A,B] ( tes tos terone) ; 17ß-O H - > C = 0
degradation [A, B] ( tes tosterone) ; 17/3-O H - » C = 0
degradation [A,B] (4 -androstene - 3 , 1 7 -dione)
degradation [A,B] ( tes tosterone) ; 17/3-O H — C = 0
degradation [A,B] (progesterone)
degradation [A,B] (progesterone)
degradation [A,B] (progesterone)
1
Δ ; enol.
1
Δ ; enol.
1
Δ ; enol.
1
Δ ; enol.
9 ( 1 1 ) Δ ; 14α-Η-+14/3-Η
1
Δ ; enol.
1
Δ ; enol.
1
Δ ; enol.
Δ ; enol. ; 16α-OH— 1 6 - C = 0
Δ ; enol. ; 16/3-OH->16-C=0
YIELD %
2
12
13
—
2-10
—
—
—
-
> 6 0
-
< i
—
-
67
ORGANISM
Nocardia r e s t r i c t u s
Nocardia r e s t r i c t u s
Nocardia r e s t r i c t u s
Nocardia r e s t r i c t u s
Mycobacter ium smegmat i s
Mycobacterium smegmat i s
Mycobacter ium smegmat i s
Corynebacter ium s implex
Septomyxa affinis
Corynebacter ium simplex
Corynebacter ium s implex
Septomyxa affinis
Corynebacter ium simplex
Glomerel la fusaroides
Corynebacter ium simplex
Septomyxa affinis
Nocardia coral l ina
Nocardia coral l ina
Nocardia coral l ina
CONSTANTS m.p.° [α]Ό
124-127
128.5-130.5
110-111.5
109-110
110-114
90-93
112-116
—
—
-
237-240
-
250-252
-
-
244.5-246
+ 24[c]
"
+121[c]
—
—
+ 79[c]
+ 86[c]
—
—
-
+29 5 [c]
-
+299[e]
-
-
-
R E F .
W-1063
W-1063
S-895
W-1063
S-821
S-819
S-821
R-762
P-709
Z-1127
Z-1126; Z-1127
B-72
B-72
L-494
R-762
P-709
S-793a
S-793a
S-793a
81
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C18H2202
1 ^18"22^3
NAME O F REACTION PRODUCT
3 -hyd roxy - l , 3 , 5 (10 ) -e s t r a t r i en -17 -one (estrone)
18 -no r -13a -H- l l j 3 -hyd roxy-1 ,4 -and ro -stadiene -3 ,17-d ione
TRANSFORMATION
3-OAc-^3-OH
3 - O P r ^ 3 - O H
3-OBu^3-OH
17/3-OH—17-C=0
d,I-17/3-OH— d - 1 7 - C = 0 + 1-17/3-OH
1
Δ ; enol. ; 17/3-OH^17-C=0
4 ,
Δ (5α); enol.
1
Δ ; r e v e r s e aldol (formaldehyde t ); enol.
17/3-Ac->17-C=0; 13/3-COOH^13a-H;
Δ1
YIELD %
17
17
18
32
-
50
t r .
95
-
-
—
60
22
-
67
55
-
-
-
—
20
ORGANISM
Saccharomyces ce rev i s i ae
Saccharomyces ce rev i s i ae
Saccharomyces ce rev i s i ae
Bac te r ium s te ro id ic las ium
Corynebacter ium sp.
Micrococcus dehydrogenans
P roac t inomyces e ry thropol i s
S t reptomyces albus
St reptomyces d ias ta t icus
St reptomyces r i m o s u s
St reptomyces albus
Baci l lus sphaer icus
Corynebacter ium s implex
Nocardia cora l l ina
Pseudomonas t e s tos t e ron i
Septomyxa affinis
Pseudomonas t e s tos t e ron i
Ar throbac te r s implex
Nocardia cora l l ina
Pseudomonas cruciviae
Pseudomonas dacunhae
Pseudomonas sp.
F u s a r i u m solani
CONSTANTS m.p.° [a]D
-
-
-
254-255
-
254
-
-
-
-
257-259
262-264
258-262
-
253-256
-
-
260-262
260-262
260-262
260-262
260-262
248-251
-
-
-
-
-
—
-
-
-
-
+161
+162[d]
-
-
+154[d]
-
-
-
-
—
*
R E F .
M-539
M-539
M-539
A-23
Z-1133
M-546
T-1034
W-1082
S-835; V-1048
S-835; U-1048
W-1102
G-317
K-487
H-399
L-507; L-508
M-573; W-1072
L-508
M-597
M-597
M-597
M-597
D-169; D-171; M-597
U-1044
82
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C18H2203
NAME OF REACTION PRODUCT
18-£Or-13j3-H-llj3-hydroxy-1,4 -andr ostadiene - 3 , 1 7 -dione
3 , 7 ö - d i h y d r o x y - l , 3 , 5 ( 1 0 ) -e s t r a t r ien -17 -one
3 ,15a -d ihydroxy- l , 3 ,5 (10 ) -e s t r a t r i en -17-one
3 ,16a -d ihydroxy- l , 3 ,5 (10 ) -e s t r a t r ien -17 - one
TRANSFORMATION
17j3-Ac-^17-C=0; 13/3-COOH^13/3-H;
Δ 1
7a -OH
7a-OH; 17/3-OH^17-C=0
15a-OH
15a-OH; 17/3-OH->17-C=0
16a -OH
16a -OH; 17 /3-OH-17-C=0
YIELD %
6
2
15
2 1 0
3
-
-
-
-
32
-
5
5
-
-
-
-
-
-
-
ORGANISM
Fusa r ium solani
Aspergi l lus ca rneus
Glomerel la cingulata
Glomerel la fusaroides
Glomerel la fusaroides
Glomerel la glycines
Glomerel la glycines
Aspergi l lus ca rneus
Glomerel la fusaroides
Glomerel la glycines
Aspergi l lus ca rneus
F u s a r i u m moniliforme
Glomerel la cingulata
Glomerel la fusaroides
Glomerel la fusaroides
Glomerel la glycines
Glomerel la glycines
Aspergi l lus ca rneus
Glomere l la fusaroides
St reptomyces cal ifornicus
St reptomyces hals te dii
S t reptomyces mediocidicus
St reptomyces halstedi i
S t reptomyces mediocidicus
CONSTANTS m.p.° [α]Ώ
199-202
-
260-262
258-260
258-260
—
-
-
-
232-233
-
228-230
228-230
-
228-230
-
-
214-216
-
-
*
-
+ l l l [ e +117[d
-
-
-
-
-
-
+212[e]
-
+197[e]
+202[e;
-
-
-
-
+175[m]
-
-
R E F .
U-1044
L-497
L-494
L-497
L-494
L-497
L-494
L-497
L-497
L-497
L-497
C-139
L-494
L-497
L-494
L-494
L-497
L-497
L-497
L-491
K-448
K-448
K-448
K-448
83
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
Cx 8H2203
C l 8H2402
NAME OF REACTION PRODUCT
3-hydroxy-D-homo-17a-oxa-1,3,5(10)-estratrien-17-one
1,3, 5(10)-estratriene-3,17/3-diol (estradiol)
l-5a-estrene-3,17-dione
4-estrene-3,16-dione
TRANSFORMATION
17/3-Ac—* 17a-oxa-17-C=0; Δ1; enol. 1
Δ ; enol.
1 Δ ; enol.; 17j3-Ac->17/3-OH
17-C=0—170-OH
d,l-17-C=0-+ d-17/3-OH + 1-17-C=0
17-C=0-»17ß-OH; 3-OAc—3-OH
17-C=0^17ß-OH; 3-OPr—3-OH
17-C=0-*17/3-OH; 3-OBu-*3-OH
3-OPr-3-OH
A1; 17/3 -OH -^ 17-C=0
16-C=0; (via 16a-OH and 16j3-OH)
YIELD %
3
-
52
75
-
12
-
-
60-75
70
-
77
—
68
-
-
71
33
33
ORGANISM
Streptomyces lavendulae
Actinoplanes missouriensis
Corynebacterium simplex
Corynebacterium simplex
Pseudomonas testosteroni
Septomyxa affinis
Septomyxa affinis
Streptomyces lavendulae
Rhizobium sp.
Sac char omy ces cerevisiae
Saccharomyces cerevisiae
Trichomonas gallinae
Saccharomyces cerevisiae
Saccharomyces cerevisiae
Saccharomyces cerevisiae
Saccharomyces cerevisiae
Saccharomyces cerevisiae
Pseudomonas testosteroni
Bacillus megaterium
Cephalospor ium acremonium
CONSTANTS m.p.° [α]Ό
338-339
-
174-180
171-173
-
-
-
-
-
177-179.5
174
-
177-178
173-174
-
-
173-174
188-189
139.5-149.
~~
-
-
-
-
-
-
-
-
+ 83[e]
-
-
+ 82[e]
-
-
-
-
+221 [c]
5 -
REF.
G-317
M-536
K-487
C-128
L-508
M-573
W-1072
G-317
C-114
W-1085
S-806
S-830; S-829
W-1094; V-1055
M-539
M-539
M-539
M-539
L-508
S-793a
S-793a
84
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
C 1 8 H2 4 0 2
C 1 8 H2 4 0 3
NAME OF REACTION PRODUCT
4 -es t r ene -3 ,16 -d ione
4 -e s t r ene -3 ,17 -d ione
9a-hydroxy-A-nor -3-andros tene-2 ,17-d ione
D-homo-17a -oxa -A-no r -3 -andros tene-2 ,17-d ione
6ξ -hyd roxy -B-no r -4 -andros tene-3 ,17-d ione
1 l a -hydroxy-B-nor-4 -andros tene-3 ,17-d ione
10/3,17/3-dihydroxy-l,4-es t rad ien-3-one
1,3, 5(10) - e s t r a t r i e n e -3,6ß,17j3-triol
TRANSFORMATION
1 6 - C = 0 (via 16a-OH and 16j3-OH)
1 6 a - O H ^ 1 6 - C = 0
16/3-OH^16-C=0
17/3-OH—17-C=0
1 7 / 3 - A c ^ l 7 - C = 0
9a-OH; 17/3-OH->17-C=0
17/3-OH— 17/3-oxa-17-C=Q
6ξ-ΟΗ
l i a - O H
1
Δ
6/3-OH
6/3-OH; 17-C=0—17|3-OH
YIELD %
-
-
-
-
-
-
-
2
-
-
-
-
-
76
71
-
36
34
4
32
-
—
ORGANISM
Streptomyces roseochromogenus
Bacil lus mega te r ium
Cephalosporium acremonium
Streptomyces roseochromogenus
Bacil lus mega te r ium
Cephalosporium acremonium
Streptomyces roseochromogenus
Baci l lus sphaer icus
Corynebacter ium s implex
Tr ichomonas gallinae
St reptomyces lavendulae
Bac te r ium eye looxy dans
Corynebacter ium s implex
Mycobacter ium rhodocrous
Nocardia r e s t r i c t u s
Nocardia r e s t r i c t u s
Pseudomonas t es tos te ron i
Pénic i l l ium c i t r inum
Absidia orchid is
Absidia orchid is
Corynebacter ium s implex
Mor t ie re l la alpina
Mor t ie re l la alpina
CONSTANTS m.p.° [α]Ό
-
-
-
-
-
-
162-166
170-173
-
163-166
-
-
—
279-280
281-283
-
229-230
210-213
115-180
230-234
-
—
—
-
-
-
-
-
-
-
-
-
-
-
-
-
+ 46[e]
+ 76[c]
-
- 91[c]
+57.5[c]
+ 23[c]
- 28[m]
-
-
R E F .
S-793a
S-793a
S-793a
S-793a
S-793a
S-793a
S-793a
G-317
K-487
S-829
G-317
S-885
S-885
S-*885
S-885
W-1080
| I S-885
L-500; L-502
P-741
P-741
D-150
L - 4 9 3 ; L-497
L-493
85
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
^18"24^3
C18 H24°4
NAME O F REACTION PRODUCT
1,3 , 5 (10) -es t ra t r i ene-3 , 7 a , 1 7 ß - t r i o l
l , 3 , 5 ( 1 0 ) - e s t r a t r i e n e -3,15a,17j3-tr iol
1,3,5(10) - e s t r a t r i ene -3,16a,17/3-tr iol
17ß -hyd roxy -4 -e s t r ene -3 ,16 -dione
1 la -hydroxy -4 - e s t r ene -3,17-dione
12ß-hydroxy-4 -es t r ene -3,17-dione
15a-hydroxy-4-es t rene -3,17-dione
16a-hydroxy-A-nor-D-homo-17a-oxa-3 -andros tene -2,17-dione
TRANSFORMATION
7a-OH
7a-OH; 17-C=0-»17ß-OH
15a-OH
15a-OH; 17-C=0— 17j3-OH
16a-OH
16a-OH; 1 7 - C = 0 ^ 1 7 ß - O H
1 6 - C = 0 (via 16/3-OH)
l l a - O H
l l a - O H ; 17ß-OH-*17-C=0
12j3-OH; 17ß-OH->17-C=0
15a-OH; 17ß-OH->17-C=0
16a-OH
YIELD %
3
-
-
-
-
1
21(cr.)
-
-
1-2
1-2; 4
-
-
-
-
-
1
69
9
4
8
10
75
ORGANISM
Aspergi l lus ca rneus
Glomere l la fusaroides
Glomere l la glycines
Aspergi l lus ca rneus
Glomere l la fusaroides
Glomerel la glycines
Aspergi l lus ca rneus
F u s a r i u m moniliforme
Glomerel la fusaroides
Glomerel la glycines
Aspergi l lus ca rneus
Glomere l la fusaroides
Glomere l la glycines
St reptomyces hals tedi i
S t reptomyces mediocidicus
St reptomyces sp.
S t reptomyces halstedi i
Steptomyces mediocidicus
Mycosphaerel la l a t ebrosa
Aspergi l lus ochraceus
Aspergi l lus ochraceus
Col le totr ichum d e r r i d i s
Fusa r ium o r thoce ra s
Pénic i l l ium sp.
S t reptomyces roseochromogenus
CONSTANTS m.p.° [a]D
225-257
-
-
-
-
250-251
-
-
248-250
248-250
281-283
281-283
-
-
-
120-130
-
212-214
185-187
200-201
200-201
202-203
-
-
-
-
-
+150[e]
-
-
-
-
+ 56[d]
+ 56[d]
-
-
-
- 90[c]
-
+ 5[c]
+121[c]
+162[c]
+162[c]
-114[c]
R E F .
L-497
L-497
L-497
L-497
L-497
L-497
L-497
C-139
L-497
L-497
L-497
L-494; L-497
L-494; L-497
K-448
K-448
S-788
K-488
K-488
D-149
D-150
D-150
D-152
D-151
D-151
L-503
86
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C 1 8 H 2 6 0 2
^ 1 8 " 2 6 ^ 3
NAME OF REACTION PRODUCT
16a-hydroxy-4-es t ren-3-one
16/3 -hydr oxy -4 - e s t r e n - 3 -one
1/3,17/3-dihydroxy-A-nor-3-andros ten-2-one
3/3-hydroxy-5,6-oxido-B-nor-andr ostan -17 -one
3/3, l l q - d i h y d r o x y - B - n o r - 5 -andros ten-17-one
3/3,X-dihydroxy-B-nor-5-androsten -17-one
17/3-hydroxy-5a-es t rane-3 ,6-dione
6/3,17/3-dihydroxy-4-estren-3-one
10ß, 17/3-dihydroxy-4-estren-3-one
TRANSFORMATION
16a-OH
16/3-OH
16-C=0->16/3-OH
16a-OH-*16/3-OH (via 16-C = 0)
1/3-OH
5 Δ -+5ξ ,6ξ -oxide
11α-OH
X-OH
6/3-OH; Δ 4 ^ Α 5 ; ketoniz0
6β-ΟΗ
10/3-OH
YIELD %
7
-
13
2
-
-
-
-
-
-
-
-
-
17
17
1
-
29
18
16
-
46
19
t r .
1
ORGANISM
Bacil lus mega te r ium
Cephalosporium ac remonium
Streptomyces roseochromogenus
Bacil lus mega te r ium
Cephalosporium acremonium
Streptomyces roseochromogenus
Bacil lus mega te r ium
Cephalosporium acremonium
Streptomyces roseochromogenus
Bacil lus mega te r ium
Cephalosporium acremonium
Streptomyces roseochromogenus
Gnomonia f ragar iae
Rhizopus n igr icans
Rhizopus n igr icans
Rhizopus n igr icans
Rhizopus reflexus
Helminthosporium kusanoi
Rhizopus n igr icans
Rhizopus n igr icans
Rhizopus re lexus
Botryt is paeoniae
Curvular ia lunata
Helminthospor ium buchloes
Rhizopus n igr icans
CONSTANTS m.p.° [α]Ό
163-164
-
163-163.5
149-150.5
-
-
-
-
-
-
-
-
-
192-200
110-150
268-270
-
209-213
217-219
-
-
205-210
205-210
209-211
199-205
+ 21[m]
-
+20[m]
+23[m]
-
-
-
-
-
-
-
-
-
+11.5[c]
- 85[c]
- 10[e]
-
- 53[c]
- 63 [m]
-
-
+ 70[c]
+ 70[c]
-
+ 76 [m]
R E F .
S-793a
S-793a
S-793a
S-793a
S-793a
S-793a
S-793a
S-793a
S-793a
S-793a
S-793a
S-793a
L-496
P-741
P-741
P-741
M-623
D-153
P-708
M-642
M-618
D-150
D-150
D-153
P-708; M-642
87
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C 1 8 H 2 6 0 3
C 18 H 26°4
C18 H28°4
C19 H20°4
C 1 9 H 2 1 ° 3 F
1 ^19"22^"'2
C19H2202C12
NAME O F REACTION PRODUCT
11a, 17ß-d ihydroxy-4-es t ren-3 -one
l l ß , 17ß-d ihydroxy-4-es t ren-3-one
12/3,17ß-dihydroxy-4-est ren-3-one
14α, 17ß-d ihydroxy-4-es t ren-3-one
15a, 17ß-d ihydroxy-4-es t ren-3-one
15ξ , 17j3-dihydroxy-4-estren-s ' o n e
16a, 17/3-dihydroxy-4-estr en-s ' o n e
16/3,17ß-dihydroxy-4-esi ren-3-one
3/3, l l a - d i h y d r o x y - 5 | , 6ξ -oxi do - B - nor- andr o stan -17 -one
10/3, l l ß , 17ß- t r ihydroxy-4-e s t r en -3 -one
3 ß , 5 a , 6 ß - t r i h y d r o x y - B - n o r -andros tan-17-one
l l ß - h y d r o x y - 3 , 1 7 - d i k e t o -l , 4 - and ros t ad i en -18 -o i c acid (18-*l l ) - lac tone
6a -fluoro -1 ,4 -andr ostadiene -3 ,11 ,17- t r ione
9a-fluor o -17/3-hydroxy-1,4,6 -andr os ta t r i ene - 3 , 1 1 -dione
1,4 ,7 -andr os ta t r i ene - 3 , 1 7 -dione
9 a , l l ß - d i c h l o r o - l , 4 - a n d r o -stadiene -3 ,17 -dione
TRANSFORMATION
11a-OH
11/3-OH
12ß-OH
14a-OH
15a-OH
1 5 | -OH
16a-OH
16ß-OH
l i a - O H ; Δ5-^5ξ , 6 | -oxide
10/3-OH; l l ß - O H
Δ5->5ξ ,6£ -oxide-> 5a,6ß-diol
1 7 ß - A c - 1 7 - C = 0
Δ1; 1 7 ß - A c ^ l 7 - C = 0
Δ1
1 7 - C = 0 ^ 1 7 ß - O H
Δ1
Δ1
YIELD %
34
4
-
3
19
2
15
-
2
9
-
35
32
2
ca. 1
12
35
-
—
-
ORGANISM
Asper gillus ochraceus
Rhizopus n igr icans
Rhizopus ref lexus
Curvular ia lunata
Col le totr ichum d e r r i d i s
Curvular ia lunata
Helminthosporium buchloes
Mucor gr i seocyanus
Fusa r ium o r thoce ra s
F u s a r i u m o r thoce ra s
Pénic i l l ium sp.
Pénic i l l ium ur t icae
Hypomyces auran t ius
Mycosphaerel la l a tebrosa
Rhizopus n igr icans
Curvular ia lunata
Rhizopus n igr icans
F u s a r i u m solani
F u s a r i u m solani
Septomyxa affinis
Sac char omy ces ce rev i s i ae
4
Septomyxa affinis
Corynebac ter ium s implex
CONSTANTS m . p . ° [α]Ό
165-166
167-168; 185-187[p]
-
214-219
163-165
-
192-194
-
136-139
136-139
-
185-186
153-154
235-240
-
170-173
320-322d.
-
-
-
- 43[c]
- 46 [c]
-
+ 92[c]
+ 92[c]
-
+ 84[c]
-
+ 95[c]
+ 95[c]
-
+ 30[c]
+ 51[c]
- 18[e]
-
+ 61
-
-
-
R E F .
D-150
P-708
M-618
D-150
D-152
D-150
D-153
M-610
D-151
M-599
D-151
M-639
D-149
D-149; S-950
P-741
D-150
P-741
U-1044
U-1044
P-709
G-305
B-72
G-308
88
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
^19"22^ - ' 3
C 1 9H 2 2 , 0 4
C 1 9 H 2 3 0 3 C 1
^ 1 9 ^ 2 3 ^ 3 **
C 1 9 H 2 3 0 4 F
C 1 9 H 2 4 0 2
NAME OF REACTION PRODUCT
1,4 -androstadiene - 3 , 1 1 , 1 7 -t r ione
1 ,4 -and ros t ad i ene -3 ,11 ,17 -t r ione-4C1 4
17/3 -hydroxy - 1 , 4 , 6 - and ro -s t a t r i ene -3 ,11 -dione
14a -hydroxy-1 ,4 -andro -stadiene - 3 , 11 ,17- t r ione
l l /3,17/3-dihydroxy-3-keto-1,4 -andr ostadien-18 -oic acid (18—>11) lactone
9a-chlor o-11/3-hydroxy-1,4-andros tad iene-3 ,17-d ione
6 a - f l u o r o - l l ß - h y d r o x y - l , 4 -androstadiene -3 ,17 -dione
6 /3-f luoro- l l /3-hydroxy- l ,4-andros tad iene-3 ,17-d ione
6a -fluoro -17/3 -hydroxy - 1 , 4 -androstadiene -3 ,11 -dione
12a - f luo ro - l l / 3 -hydroxy- l ,4 -andr ostadiene -3 ,17 -dione
9 a - f l u o r o - l l ß , 17/3-dihydroxy-1,4,6 - andros ta t r i en -3 -one
9a -fluor o - 16a -hydroxy -4 -andr ostene -3 ,11 ,17 - t r ione
1,4 -androstadiene -3 ,17 -dione
TRANSFORMATION
17a-OH-17j3-(20-C= 0 - 2 1 - O H ) - 1 7 - C = 0 ;
Δ1
1 7 / 3 - A c ^ l 7 - C = 0 : Δ1
Δ 1 ; 17a-OH-17j3-(20-C = 0 - 2 1 - O A c ) ^ 1 7 - C = 0
17-C=0—17/3-OH
Δ1
1 1 - C = 0 (probably via 11/3-OH): 14a-OH
l l / 3 - 0 H - * l l - C = 0 ; 14a-OH
Δ 1 ; 17/3-Ac^l7/3-OH
17/3-Ac-^ 17/3-OH
17ß-(20-C=O-21-OH) ^ 1 7 - C = 0 ;
Δ1
Δ1
Δ1
Δ1
A 1 ; 17/3-OH->17-C=0
17-C=0^17/3-OH
16a-OH
Δ1
YIELD %
40
-
96
-
-
-
3
-
-
-
-
-
-
-
47
-
8
-
-
ORGANISM
Septomyxa affinis
Septomyxa affinis
Bacil lus sphaer icus
Saccharomyces ce rev i s i ae
Bacil lus sphaer icus
Pe l l i cu la r i a f i lamentosa
Pe l l icu lor ia f i lamentosa
Fusa r ium solani
Fusa r ium solani
Septomyxa affinis
Septomyxa affinis
Septomyxa affinis
Septomyxa affinis
Corynebacter ium s implex
Saccharomyces ce rev i s i ae
St reptomyces roseochromDgenus
Actinoplanes mi s sou r i ens i s
Ar throbac te r s implex
Arthrobacter sp .
Bacil lus lentus
Bacil lus pulvifaciens
Bacil lus sphaer icus
CONSTANTS m.p.° [a]D
186-190
-
-
-
300-305do
308-310d. (
305-307
310-314
-
-
-
-
-
-
-
132-135
-
141-143
143-144.5
-
-
-
-
-
+212 : - m , l : l )
-
-
-
-
-
-
-
-
-
-
-
+115[c]
-
R E F .
S-901
W-1072
C-120
G-305
T-955
T-955
T-955
U-1044
U-1044
H-399
P-709
P-709
P-709
R-772
G-305
T-1008
M-536; M-537
M-597
D-171 ; D-170
R-750
1-420
S-942; H-399; H-373
89
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C 19 H 24 0 2
NAME OF REACTION PRODUCT
l , 4 - and ros t ad i ene -3 ,17 -d ione
TRANSFORMATION
Δ1
Δ1
(from laf l 3 , 2/3-H)
Δ4
(from 5a-H)
Δ 1 ' 4
(from 5 Q - H )
17/3-OH-*17-C=0
A 1 ; 17 /3-OH^17-C=0
YIELD %
-
-
-
4
42-44
-
-
-
-
-
-
-
-
-
-
-
-8
-
-
ORGANISM
F u s a r i u m caucas icum
Fusa r ium solani
Mycobacter ium flavum
Pseudomonas dacunhae
Pseudomonas sp.
Pseudomonas t e s tos te ron i
Pycnodothis sp .
Septomyxa affinis
Bacil lus sphaer icus
Pseudomonas t e s tos te ron i
Calonectr ia decora
Fusa r ium caucas icum
F u s a r i u m solani
P ro taminobac te r alboflavum
Pro taminobac te r r u b r u m
Pseudomonas t e s tos te ron i
Cyl indrocarpon rad ic ico la
St reptomyces lavendulae
Actinoplanes sp .
Bacil lus pulvifaciens
Baci l lus sphaer icus
Corynebac ter ium s implex
Corynebac te r ium s implex
F u s a r i u m caucas icum
CONSTANTS m.p.° [α]Ώ
-
-
142-143.5
142-143.5
140.5-141 +123[c]
-
-
-
-
145-146 +110[c]
-
-
-
- -
-
-
: :
-
-
-
-
R E F .
V-1056; W-1117; C-97; H-399; W-1116; W-1118
V-1056
C-100
M-597
D-171
L-507; L-508
K-450
W-1072; H-399
B-75a; G-323
L-507; L-508
W-1096
W-1116; V-1056
V-1056
S-866
S-866
L-507; L-508
P-733
P-733
M-537
1-420
H-373
N-665
C-128
W-1118; C-97
90
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C19H2402
NAME OF REACTION PRODUCT
1,4 -andr ostadiene -3 ,17 -dione
TRANSFORMATION
Δ 1 ; 1 7 ß - O H ^ 1 7 - C = 0
Δ 1 ; 17j3-OFo — 1 7 - C = 0
Δ 1 ; 17ß-OAc->17-C=0
Δ 1 ; 1 7 j 3 - O P r - 1 7 - C = 0
3o-OH->3-C = 0 ; Δ1 ' 4 (from 5a-H)
A 1 , 4 ( f rom 5/3-H); 3a -OH-^3-C=0
17 j3 -OH->17-C=0; Δ1,4 (from 5/3-H)
Δ 1 ; 3j3-OH->3-C=0; Δ 5 - Δ 4
YIELD %
-
-
-
-
'-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
45
ORGANISM
Fusa r ium la te r i t ium
Fusa r ium solani
Mycobacter ium f la vu m
Nocardia coral l ina
Pseudomonas ch lororaphis
Pseudomonas t e s tos t e ron i
Septomyxa affinis
Fusa r ium caucas icum
Fusa r ium la te r i t ium
F u s a r i u m solani
F u s a r i u m caucas icum
F u s a r i u m la te r i t ium
F u s a r i u m solani
Fusa r ium caucas icum
Fusa r ium la te r i t ium
Fusa r ium solani
Mycobacter ium fortuitum
Mycobacter ium smegmat i s
Mycobacter ium tubercu los i s
Mycobacter ium fortuitum
Mycobacter ium smegmat i s
Mycobacter ium tubercu los i s
Pseudomonas t es tos te ron i
4ct inoplanes mi s sou r i ens i s
Bacil lus lentus
Bacil lus pulvifaciens
CONSTANTS m.p.° [a]D
- -
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
140-142 + l l l [ c ]
139.5-140
R E F .
C-97
C-97
C-100
H-399
N-648
L-507
S-835; W-1072
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
S-818
S-818
S-818
S-818
S-818
S-818
L-507
M-537; M-536
R-750
T-1027; 1-420
91
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
^19"24^2
NAME OF REACTION PRODUCT
1,4 -andr ostadiene -3 ,17 -dione
TRANSFORMATION
3ß-OH-*3-C = 0 ; Δ5->Δ4
1 Δ ; 3j3-OAc-^3ß-OH;
3jS-OH-*3-C=0; Δ —*Δ
A 1 ; 3/3-OH-^3-C = 0 ; 17 /3-OH^17-C=0; Δ 5 - Δ 4
1 Δ ;
17j3-Ac-*17-C=0
YIELD %
-
-
—
-
-
17
-
-
-
80
-
-
-
-
-
27-37
39
7
ORGANISM
Fusa r ium caucas icum
F u s a r i u m caucas icum
Mycobacter ium fortuitum
Mycobacter ium smegmat i s
Mycobacter ium tubercu los i s
Bacil lus lentus
Baci l lus pulvifaciens
Corynebacter ium Simplex
Calonectr ia decora
Cylindrocarpon rad ic ico la
Fusa r ium caucas icum
F u s a r i u m caucas icum
Fusa r ium la t e r i t ium
F u s a r i u m solani
Fusa r ium solani
F u s a r i u m solani
Mycobacter ium f la vu m
Mycobacter ium smegmat i s
Pycnodothis sp .
Septomyxa affinis
Septomyxa affinis
St reptomyces lavendulae
S t rep tomyces lavendulae
CONSTANTS m.p.° [α]Ό
-
-
- -
- -
140-142 +112[c]
139-140 +110[c]
-
145-146 +110
-
145-146 +110[c] +112[a]
140-141
-
-
-
139-140 +119[c]
143-144.5 +115[c]
-
138-139.5 +115[c]
REF .
W-1118
V-1056
S-818
S-818
S-818
R-750
1-420
N-665 ; C-128
V-1053
P-733
V-1056
W-1116; W-1117; W-1118; C-97
C-97
W-1095; V-1056
N-663
S-949; C-97
C-100
S-820
K-450
W-1072
S-901
F-284; F-271
P - 7 3 3 ; P-719
92
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C19H2402
NAME OF REACTION PRODUCT
1,4 -andr ostadiene -3 ,17 -dione
TRANSFORMATION
A1; A 1 6 - 1 7 - A c ^ l 7 - C = 0
1
A : 16α, 17α -oxido-17/3-Ac—17-C=0
1
A ; 1 la -OH -17/3 -Ac— 1 7 - C = 0
A1; 17j3(-20-C=O-21-OH) ->17-C=0
Δ 1 ; 17ß(-20-C=O-21-F) - 1 7 - C = 0
Δ 1 ; 17a-OH-17j3(-20-C=0-21-OH) — 1 7 - C = 0
A 1 ; 17ß-(20/3-OH-21-H)
- 1 7 - C = 0
« 4 Δ ' ;
Δ — Δ 4 ; 17/3-Ac— 1 7 - C = 0 ; 3 ß - O H - 3 - C = 0
Δ 5 - Δ 4 ; Δ1; Δ 1 6 - 1 7 - Α ο - 1 7 - Ο = 0 ; 3/3-ΟΗ—3-C=0
Δ ^ ' - ί δ α - Η ) ; 17ß-Ac-*17-C=0
Δ1 , 4-(5α-Η); Δ 1 6 -17-Αο-*17-Ο=0
Δ ' ^ - ί δ α - Η ) ; 3j3-OH—3-C=0; 17ß-Ac->17-C=0
Δ ^ ^ ί δ α - Η ) ; 3 /3 -OAc-3-C=0 · 17|3-Ac-»17-C=0
YIELD %
-
-
—
42
-
-
-
40
46
10-15
—
_
-
-
-
-
ORGANISM
Fusa r ium caucas icum
Pycnodothis sp.
Fusa r ium caucas icum
Septomyxa affinis
Fusa r ium caucas icum
Fusa r ium solani
Mycobacter ium f la vu m
Pycnodothis sp.
Septomyxa affinis
Septomyxa affinis
Septomyxa affinis
Septomyxa affinis
Mycobacter ium f la vu m
Fusa r ium caucas icum
Fusa r ium solani
Fusa r ium caucas icum
Fusa r ium caucas icum
Fusa r ium solani
Fusa r ium caucas icum
Fusa r ium caucas icum
Fusa r ium caucas icum
Fusa r ium solani
CONSTANTS m . p . ° [ÛÎ]D
-
-
"
"
~
- -
-
-
-
- -
~ -
-
-
-
-
—
R E F .
W-1118
K-450
W-1118
S-901
W-1118; V-1056
V-1056
C-100
K-450
W-1072
S-901
S-901
S-901
C-100
W-1118; V-1056
V-1056; W-1095
W-1118
W-1116; W-1118; V-1056
V-1056; W-1095
W-1118
W-1118
V-1056
V-1056 1
93
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C19H2402
1 ^19^24^2 *2
C19H2402N2
C 19 H 24°3
NAME O F REACTION PRODUCT
l , 4 - a n d r o s t a d i e n e - 3 , 1 7 - d i o n e
1,4 -andr ostadiene - 3 , 1 7 -dione-1-H3
1 7 ß - h y d r o x y - l , 4 , 9 ( l l ) -andros t a t r i en -3 -one
3-hydroxy-2-methy l -1,3,5(10) - e s t r a t r i e n - 17-one
3-hydroxy-4-methyl -1,3,5(10) - e s t r a t r i en -17 -one
16 ,16 -d i f l uo ro - l , 3 ,5 (10 ) -e s t r a t r i e n e - 3 , 1 7 a - d i o l - 3 -methyl e ther
16 -d i azo -4 -and ros t ene -3 ,17 -dione
17ß-hydroxy-1 ,4 -andro -stadiene -3 ,11 -dione
2 -hyd roxy -1 ,4 - and ro -s tad iene-3 ,17-d ione
6 o -h y d ro xy -1 ,4 - and ro -stadiene -3 ,17 -dione
6ß -hyd roxy -1 ,4 -and ro -stadiene -3 ,17 -dione
1 l a - h y d r o x y - 1 , 4 - a n d r o -stadiene - 3 , 1 7 - dione
TRANSFORMATION
17ß-(2' -isooctyl) - 1 7 - C = 0 ; 3ß-OH-> 3-C = 0 ; Δ*—Δ«; Δ ' Δ1
17-C=0-^17ß-OH
A1(2a-CH3); enol . ; 1 7 ß - O H - 1 7 - C = 0
Δ1; enol.; 17ß-OH->17-C=0
1 7 - C = 0 - ^ 1 7 ö - 0 H
3ß-OH—3-C=0; Δ 5 ->Δ 4
A 1 ; 17ß-Ac->17ß-OH
A 1 ; 17α-ΟΗ-17β(-20-C = 0 - 2 1 - O H ) - ^ 17β-ΟΗ
Δ 1 , 4 - ( 5 α - Η ) ; 1 7 ß - A c ^ l 7 ß - O H
Δχ-(2α-ΟΗ); 17ß-OH->17-C=0
Δ 1 -(2α-ΟΗ); 2o-OAc-»2a-OH; 17ß-OAc->17-C=0
Δ 1 -(2β-ΟΗ); 2ß-OAc->2ß-OH; 17ß-OAc-*17-C=0
3ß-OH->3-C = 0 ; Δ 5 - Δ 4 ; Δ 1 ; 6α-ΟΗ
3β-ΟΗ—3-C=0; A W ; Δ 1 ; 6β-ΟΗ
11α-ΟΗ
1 7 ß - A c ^ l 7 - C = 0
Δ1 ; Π α - Ο Η ; 1 7 ß - A c ^ l 7 - C = 0
YIELD %
-
—
55
17
13
35(cr„)
-
—
9
29
-
13
-
-
"
"
37
~
14
ORGANISM
No card ia sp.
Baci l lus sphaer icus
Saccharomyces ce rev i s i ae
Septomyxa affinis
Septomyxa affinis
F lavobac ter ium dehydrogenans
Flavobacter iu m dehydrogenans
Septomyxa affinis
Septomyxa affinis
Hypomyces haematococcus
Septomyxa affinis
Bacil lus sphaer icus
Nocardia coral l ina
Baci l lus sphaer icus
Nocardia coral l ina
Nocardia cora l l ina
Actinoplanes mi s sou r i ens i s
Actinoplanes mi s sou r i ens i s
Sporot r ichum bombycinum
Fusa r ium javanicum
Septomyxa affinis
F u s a r i u m javanicum
CONSTANTS m.p.° [a]D
-
—
145-148
243-244
244-247
111-113
217-218
—
208-210d.
233.5-2340
-
148-150
-
~
255-259
200-204
212-214
190-192
-
-
- 28[dl
+167[cl
+147[c]
+ 48[d]
-112[dl
-
5 +169
-
+ 67[c]
-
-
—
"
-
+86. 5[c]
+ 79[c]
R E F .
W - l l l l
B-75a
R-775
P-731
P-731
R-774
R-763
W-1072
S-901
M-574
M-574
G-318; H-373
H-399
H-399
H-399
H-399
M-536; M-537
M-536; M-537
M-582
F-276
W-1072
F - 2 7 8 ; F-274
94
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C19H2403
NAME OF REACTION PRODUCT
1 l a - h y d r o x y - 1 , 4 - a n d r o -stadiene -3 ,17 -dione
l l / 3 - h y d r o x y - l , 4 - a n d r o -s tadiene-3 ,17-dione
1 4 a - h y d r o x y - l , 4 - a n d r o -stadiene -3 ,17 -dione
D - h o m o - 1 7 a - o x a - l , 4 - a n d r o -stadiene -3 ,17 -dione
TRANSFORMATION
170-OH->17-C=O
Δ1
A 1 ; 17/3-Ac-^17-C=0
A 1 ; 17/3-(20-C=O-21-O H ) - 1 7 - C = 0
17α-ΟΗ-17β-(20-C = 0-21-OH)-> 1 7 - C = 0
1
17α-ΟΗ-17β-(20-C=0-21-OH)-> 1 7 - C = 0
Δ1
1
Δ 5 - ^ Δ 4 ; Δ ;
3 /3 -OH^3-C=0 ; 14α-OH
Δ1
17-C=0->17a-oxa-1 7 - C = 0
17/3-OH-*17a-oxa-1 7 - C = 0
A 1 ; 17 -C=0-»17a -oxa -1 7 - C = 0
A 1 ; 17j3-OH-*17a-oxa-1 7 - C = 0
YIELD %
-
70-80 ( c r . )
-
55
—
-
-
60
-
-
-
-
-
-
-
-
-
-
ORGANISM
Actinoplanes mi s sou r i ens i s
Corynebacter ium simplex
Septomyxa affinis
Septomyxa affinis
Pseudomonas chlororaphis
Pseudomonas ch lororaphis
Bacil lus pulvifaciens
Bacil lus pulvifaciens
Bacil lus lentus
Cylindrocarpon radic icola
Fusa r ium caucas icum
Cylindrocarpon radic icola
Fusa r ium caucas icum
Fusa r ium la te r i t ium
Fusa r ium solani
Septomyxa affinis
Cylindrocarpon radic icola
Fusa r ium caucas icum
F u s a r i u m la te r i t ium
F u s a r i u m solani
Hypomyces solani
Septomyxa affinis
CONSTANTS m.p.° [α]Ό
-
176-179
-
185-186
—
-
284-287d„
207.5-208
219-220
-
-
-
-
216-218
-
-
-
-
-
-
—
-
—
-
-
+ 69[ai
- 45
-4901
-
-
-
-
- 46[c]
-
-
-
-
-
R E F .
M-536
C-128 ; N-666 ; N-667
W-1072
S-901
N-648
N-648
1-420
S-792; 1-420
R-750
P-733
W-1095
P-733
C-97
C-97
C-97
W-1072
F - 2 6 9 ; F - 2 7 4 ; F-284
C-97
C-97
C-97
L-525
W-1072
95
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
^ 1 9 " 2 4 ^ 3
NAME OF REACTION PRODUCT
D - h o m o - 1 7 a - o x a - l , 4 - a n d r o -s tad iene-3 ,17-d ione
TRANSFORMATION
1 7 ß - O F o ^ 17a -oxa -17 -C=0
1 Δ ;
17/3-OAc— 17a -oxa -17 -C=0
1
Δ ; 17 /3 -OPr^ 17a -oxa -17 -C=0
17ß-Ac-> 1 7 a - o x a - 1 7 - C = 0
A 1 ; 17a-OH-17/3-Ac^ 1 7 a - o x a - 1 7 - C = 0
Δ 1 ; 17/3-(20-C=O-21-O H H 1 7 a - o x a - 1 7 -
c=o A 1 ;
17/3-(-20-C=O-21-F) -+17a-oxa -17-C=0
A 1 ; 17α-ΟΗ-17β-(20-C = 0 - 2 1 - O H H 17a-oxa=17=C=0
YIELD %
-
-
-
-
-
-31-50
-
33
-
75
-
21
-19
60
20
35
ORGANISM
Fusa r ium caucas icum
Fusa r ium la te r i t ium
F u s a r i u m solani
Fusa r ium caucas icum
Fusa r ium la te r i t ium
F u s a r i u m solani
F u s a r i u m caucas icum
Fusa r ium la te r i t ium
Fusa r ium solani
Cylindrocarpon radic icola
Fusa r ium caucas icum
Fusa r ium javanicum
Fusa r ium la te r i t ium
Fusa r ium solani
F u s a r i u m solani
Septomyxa affinis
Septomyxa affinis
Septomyxa affinis
Fusa r ium solani
Fusa r ium solani
Septomyxa affinis
Cylindrocarpon rad ic ico la
CONSTANTS m . p . ° [α]Ό
-
-
-
-
-
-218-219
~~
220-222
-
213-215
-
-
221-223
~
-
~
-
-
-
-
-
-- 44[c]
-
- 47[cl
-
- 44[c]
-
-
-
-
-
-
REF.
C-97
C-97
C-97
C-97
C-97
C -97
C-97
C-97
C-97
F - 2 6 9 ; F - 2 7 4 ; F - 2 8 4 ; P-733
E-202 ; C-97 ; W-1116
F - 2 7 4 ; F-278
C-97
K-462; N-663
S-949; C-97
S-901
W-1072
S-901
K-462
S-901
S-901
F - 2 6 9 ; F - 2 7 5 ; F-284
96
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
j EMPIRICAL FORMULA
C 19 H24°3
NAME OF REACTION PRODUCT
D-homo-17a -oxa -1 ,4 - and ro -s tadiene-3 ,17-dione
1 Iß , 17ß-dihydroxy- l , 4 ,6 -andros ta t r i en-3-one
9 ,10 - seco-3 -hydroxy-1,3, 5(10)-andros ta t r iene-9,17-dione
1 -5a -andros t ene -3 ,11 ,17 -t r ione
TRANSFORMATION
17α-ΟΗ-17β-(20-C=0-21-OH)-> .17a-oxa-17-C=0
1
Δ 5 - Δ 4 ; ' 3ß-OH->3-C = 0 ; 17j3-(20-C=O-21-O A c ) - 4 7 a - o x a - 1 7 -c=o Δ 1 , 4 - ( 5 α - Η ) ; 17ß-Ac-+17a-oxa-1 7 - C = 0
17-C=0->17ß-OH
1 Δ ; reVc a ldol ; enoL
9a-OH; Δ 1 ; r ev . a ldol ; enol.
9a-OH; Δ1; r ev . aldol; e n o l ; 17/3-O H - 1 7 - C = 0
9α-ΟΗ;Δ*; rev0 aldol; enol. ; 17β-A c ^ l 7 - C = 0
9α-ΟΗ;Δχ; Δ 5 -+Δ 4 ; 3ß-OH-> 3-C = 0 ; reve aldol; enol0
9a-OH; 3 a - O H ^ 3 - C = 0 ; Δ 1 , 4 - ( 5 α - Η ) ; reVo aldol; enol„
9a-OH; 3 a - O H - > C = 0 ; Δ 1 Μ - ( 5 β - Η ) ; r ev . aldol; enol.
1 7 ß - A c - > 1 7 - C = 0 ; Δ1
YIELD %
-
46
10
ca0 20
-1
26
1
<1
—
ORGANISM
Pseudomonas ch lora raphis
Fusa r ium solani
Fusa r ium caucas icum
Saccharomyces ce rev i s i ae
Ar throbac te r sp .
Bacil lus sphaer icus
Ar throbac ter sp .
Nocardia coral l ina
Nocardia coral l ina
Nocardia r e s t r i c t u s
Pseudomonas sp.
Nocardia r e s t r i c t u s
Mycobacter ium smegmat i s
Mycobacter ium sp .
Mycobacter ium spc
Mycobacter ium sp .
Septomyxa affinis
CONSTANTS m.p.° [a]D
~
-
123-129
122-129
120-126
145.5-147
124-129
122-124
123.5-125
122-124
—
—
—
-
+ 96[cl
-
-
--
+100.5[c
—
-
~
"
R E F .
N-648
K-462
W-1116
G-305
D-170;
D-172
K-473 D - 1 7 1 ; M-597
D-172; M-597
M-597
S-895;
D-169; D - 1 7 1 ; M-597
W-1063
S-820
S-818
S-818
S-818
W-1072
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
97
EMPIRICAL FORMULA
C19 H24°3
C19 H24 04
NAME OF REACTION PRODUCT
l - 5 a - a n d r o s t e n e - 3 , 1 1 , 1 7 -t r ione
1 - 5j3 -andr ostene - 3 , 1 1 , 1 7 -t r ione
9û, 1 l a -oxido -4 -andr ostene -3,17-dione
4 -andr os tene - 3 , 6 , 1 7 - t r ione
4 -andr ostene - 3 , 6 , 1 7 - t r ione -7-H3
4 -andr ostene - 3 , 1 1 , 1 7 - t r ione
unknown
1 l a -hydr oxy-D-_homo -17a-oxa -1 ,4 -andr ostadiene -3,17-dione
15a -hydr oxy -D-homo -17a -oxa -1 ,4 -and r ostadiene -3,17-dione
16a -hydr oxy -D-homo-17a-oxa -1 ,4 -andr ostadiene -3,17-dione
3 ,18 -d ihyd roxy -9 ,10 - seco -1,3,5(10)-andr o s t a t r i e n e -9,17-dione
14a-hydroxy-4-andros tene -3 ,11 ,17 - t r ione
TRANSFORMATION
17/3-Ac-*17-C=0
17ß-Ac->17-C=0; Δ1
1 Δ ;
1 7 ß - A c - 1 7 - C = 0
Δ —>9α,11α-oxido
6 - C = 0
6 - C = 0 (via 6j3-OH)
llj3-OH— 11-C = 0
17/3-OH^17~C=0
1 7 j 3 - A c ^ l 7 - C = 0
17α-ΟΗ-17β-( 2 0 - C = O - 2 1 - O H ) ^ 17-C = 0
17a-OH-17/3-( 2 0 - C = O - 2 1 - O A c H 1 7 - C = 0
unknown
17/3 -Ac -> 1 7 a - o x a - 1 7 - C = 0 ; 11a-OH
15a-OH
16a-OH
A 1 ; r ev . aldoL enolQ
14a-OH
YIELD %
28-45
-
5-10
53
-
2
-
-
-
-
-
-
-
0 .3 -5
< 1
42
45
~
ORGANISM
Septomyxa affinis
Septomyxa affinis
Septomyxa affinis
Nocardia sp.
Euglena g rac i l i s
Rhizopus a r r h i z u s
Gibberel la saubinett i
Tr ichomonas gallinae
Aspergi l lus o ryzae
Gliocladium catenulatum
Pénic i l l ium expansum
Gliocladium catenulatum
Pénic i l l ium l i lacinum
Gliocladium catenulatum
Pénic i l l ium l i lacinum
Bacil lus pulvifaciens
F u s a r i u m javanicum
Pénic i l l ium sp.
S t reptomyces roseochromogenus
Baci l lus sphaer icus
Pe l l i cu la r i a f i lamentosa
CONSTANTS m.p.° [α]Ό
2440 5-246.5
-
174.5-177.5
273-275
-
205-208
-
-
-
-
-
-
-
284-287
251-253
260-262
196-198; 213-214
148-150
"
+188[c]
-
+205[c]
+180[c]
-
-
-
-
-
-
-
-
-
-
- 58[c]
- 55[c]
- 68[c]
+ 91[c]
"
REF.
E -207 ; M-573
W-1072
E-207 ; M-573
S-886
G-322
B-32
U-1043
S-829
C-102
M-633
M-637
M-633
M-637
M-633
M-637
T-1027
F - 2 7 4 ; F-278
D-158; P-706
T-1000; P-706
K-473
K-473
98
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C 19 H 24 0 4
C19H2502F
C 1 9 H 2 5 ° 3 F
C19H2504F
C 19 H26°2
NAME OF REACTION PRODUCT
14a-hydroxy-4-androstene -3 ,11 ,17- t r ione
15a-hydroxy-4-androstene -3 ,11 ,17- t r ione
6a - fluor o - 17a -methyl -1,3, 5(10) - e s t r a t r i ene -3,17j3-diol
9a-fluoro-ll j3,17/3-dihydroxy-1,4 -andr ostadien - 3 -one
12a-fluoro-l l /3,17/3-d ihydroxy-1 ,4 -andro -Stadien-3-one
9a -fluoro -1 1/3 -hydroxy -4 -andros tene-3 ,17-d ione
9a- f luoro- l l /3 ,16a-d ihydroxy-4 -andr ostene -3 ,17 -dione
1 7 ß - h y d r o x y - l , 4 - a n d r o -s tadien-3-one
TRANSFORMATION
14a-OH; l l / 3 - O H ^ l l - C = 0
n-c=o
Δ ; enoL
17-C=0^17/3-OH
Δ1
17 j3 -Ac-17-C=0
16a-OH
Δ1
17-C=0-*17/3-OH
A 1 ; 1 7 - C = 0 - 1 7 ß - O H
YIELD % -
~
-
-
-
58(cr0)
57(cr . )
21
-
-
---
--
---
84
82
-
-
-
ORGANISM
Pel l i cu la r ia f i lamentosa
Pe l l i cu la r ia fi lamentosa
Septomyxa affinis
Saccharomyces ce rev i s i ae
Corynebacter ium simplex
Cylindrocarpon radic icola
St reptomyces roseochromogenus
St reptomyces roseochromogenus
Corynebacter ium s implex
Corynebacter ium s implex
Fusa r ium caucas icum
Fusa r ium la te r i t ium
Fusa r ium solani
Mycobacter ium smegmat i s
Nocardia cora l l ina
Pseudomonas t es tos te ron i
Ramula r i a robus ta
Septomyxa affinis
Volutella ci l iata
Saccharomyces ce rev i s iae
Saccharomyces ce rev i s i ae
Tr ichomonas gallinae
Fusa r ium caucas icum
Fusa r ium la te r i t ium
CONSTANTS m . p . ° [û?]D
301-304do
199-201
-
_
—
260-262
280-282
262-270
159-165
165-167
-
---
--
---
168
163-167
-
-
-
+263 | c ; m - l : l ]
-
-
-
—
+ 177[c'|
+173[c|
+ 157[m]
-
~
-
---
--
----
-
—
-
-
R E F .
T-955
T-955
C-93
# - 6 6 6
R-772
T-996
T-1008
B-62
N-665
C-128
C-97
C-97
C-97
S-873
H-399
L-507
L-525
W-1072
L-525
D-143
C-128
S-829
C-97
C-97
99
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
| C19H2602
NAME OF REACTION PRODUCT
17/3 -hy dr oxy -1 ,4 - and ro -s tadien-3-one
TRANSFORMATION
Δ 1 ; 17-C = 0 - 1 7 / 3 - O H
4
Δ ; 17-C=0->17ß-OH
Δ 1 , 4 - (5β-Η)
Δ 1 , 4 - ( 5 α - Η ) ; 1 7 - C = 0 - 1 7 / 3 - O H
1 5 4
Δ ; Δ —Δ ; 3/3-OH-3-C = 0
ι Δ ; 17/3-AC-17/3-OH
1
Δ ; 17j3-(20j3-OH-21-H) ^17/3-OH
Δ ; 17a-OH-17/3-Ac^ 17/3-OH
ι Δ ; 17/3-(20-C=O-21-
ΟΗ)-17/3-OH
1
Δ ; 17/3-(20-C=O-21-F) ->17β-ΟΗ
1
Δ ; 17a-OH-17/3-(20-C= 0-21-OH)->17ß-OH
YIELD %
Γ -
-
-
-
-
7
-
-
-
-
--
8
18
12
~
50
14
20
11
<ι
ORGANISM
Fusa r ium solani
Mycobacter ium f la vu m
Pseudomonas tes tos te roni
Septomyxa affinis
Pseudomonas t es tos te ron i
Pseudomonas tes tos te ron i
Pseudomonas t es tos te ron i
Corynebacter ium s implex
Cylindrocarpon radic icola
Fusa r ium caucas icum
Fusa r ium la te r i t ium
Fusa r ium solani
Fusa r ium solani
Mycobacter ium f la vu m
Septomyxa affinis
Septomyxa affinis
St reptomyces lavendulae
Mycobacter ium f la vu m
Septomyxa affinis
Septomyxa affinis
Mycobacter ium f la vu m
Septomyxa affinis
Septomyxa affinis
Septomyxa affinis
Septomyxa affinis
CONSTANTS m.p.° [a]D
_
-
~
-
-
-
164-166 4-25|c |
-
-
-
-
167-168
-
172-173 + 23
-
167-168 +21[c ]
~ ~~
-
— -
- _
REF.
C-97
C-100
L-508
W-1072
L-508
L-508
L-508
N-665 ; C-128
P-733
C-97
C-97
C-97
N-663
C-100
W-1072
S-901
F - 2 8 4 : F -271 : P-733
C-100
W-1072
S-901
C-100-
W-1072
S-901
S-901
S-901
100
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C19 H26 0 2
NAME OF REACTION PRODUCT
1-5« -andr ostene -3 ,17 -dione
1 -5/3 -andr ostene -3 ,17 -dione
4 -andros tene-3 ,17-d ione
TRANSFORMATION
1 Δ
Δ1 - ( la-H2)
ΔΧ-(1α-Η3)
1
* ; 17/3-OH-17-C=0
Δ 4 - 5 β - Η
1 7 ß - O H - 1 7 - C = 0
3j3-OH— 3 - C = 0 ; Δ 5 - Δ 4
YIELD %
-
-
-
-
80
6
-
-
-
—
-
-
-
-
47
-
-
-
1
-
18
-
47
-
87
ORGANISM
Bacil lus sphaer icus
Bacil lus sphaer icus
Bacil lus sphaer icus
Baci l lus sphaer icus
Clos t r id ium paraputr i f icum
Aspergi l lus oryzae
Bacil lus pulvifaciens
Cladosporium r e s inae
Corynebacter ium s implex
Fusa r ium caucas icum
Fusa r ium la te r i t ium
Fusa r ium solani
Nocardia coral l ina
Pénic i l l ium l i lacinum
Proac t inomyces ery thropol i s
Pseudomonas chlor or aphis
Pseudomonas t es tos te ron i
Tr ichomonas gallinae
Wojnowicia graminis
Acetobacter pas teur ianu m
Baci l lus pulvifaciens
Corynebacter ium helvolum
Corynebacter ium simplex
Flavo bac te r ium androstenedionicum
Micrococcus dehydrogenans
CONSTANTS m.p.° [α]Ώ
-
-
-
-
168-169
167-169
-
-
-
-
-
-
-
-
171
-
-
-
160-167
173
169-170
-
167-169
-
168-169
-
-
-
-
+222[el
-
-
-
-
-
-
-
-
-
-
-
-
-
-
_ +198[c]
+216[c]
-
-
-
-
R E F .
H-373
R - 7 6 8 ; R-769
G-323 ; B-75a
H-373
S-824
K-482
1-420
F-254
C-128
C-97
C-97
C-97
H-399
P-737
T-1032
N-648
L-508
S-829
H-381
K-457
T-1027 ; 1-420
M-546
N - 6 6 5 ; C-128
E-219
E-214
101
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C19H2602
NAME OF REACTION PRODUCT
4-andros tene -3 ,17-d ione
TRANSFORMATION
3 /3 -OH^3-C=0 ; Δ —»Δ
3/3-OAc->3-C=0; Δ5->Δ4
3 ß - O H - 3 - C = 0 ; Δ 5 - Δ 4 ; 17/3-OH-*17-C=0
3a -OH->3-C=0 ; Δ4-(5α-Η)
3 a - O H ^ 3 - C = 0 ; Δ4-(5β-Η)
17ß-OH->17-C = O j Δ4-(50-Η)
1 7 / 3 - A c ^ l 7 - C = 0
YIELD %
70
-
-
96
84
-
40
18
4
6
76
-
-
-
-
-
-
-
-
—
ORGANISM
"Milan y e a s t "
Mycobacter ium fortuitum
Mycobacter ium smegmat i s
Mycobacter ium tuberculos is
P roac t inomyces ery thropol is
St reptomyces globisporus
Streptomyces v i r idochromogenes
Corynebacter ium s implex
Corynebacter ium sp0
Fla vo bac te r ium androstenedionicum
Fla vo bac te r ium carboni l icum
Micrococcus denydrogenans
P roac t inomyces ery thropol is
S t reptomyces globisporus
St reptomyces v i r idochromogenes
Mycobacter ium fortuitum
Mycobacter ium smegmat i s
My cobacter ium tubercu los i s
Mycobacter ium fortuitum
Mycobacter ium smegmat i s
Mycobacter ium tubercu los i s
Pseudomonas t es tos te ron i
Aspergi l lus cheval ie r i
CONSTANTS m.p.° [ a ] p |
168-169
_
-
169
171-172 +192[cl
- -
165-169
170-171
167-168
170
- -
~ —
- -
- -
— —
-
-
-
-
"
R E F .
M-552
S-818
S-818
S-818
T-1032
H-335
H-335
C-128
Z-1133
E-220 ; E-219
M-592
E-217
T-1032
H-337
H-337
S-818
S-818
S-818
S-818
S-818
S-818
L-508
C-102
102
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C19H2602
NAME OF REACTION PRODUCT
4-andros tene-3 ,17-d ione
TRANSFORMATION
17j3-Ac—17-C=0
17/3-Pr->17-C=0
17a-OH-17j3-Ac-17-C = 0
17j3-(20-C=O-21-O H ) - 1 7 - C = 0
YIELD %
-
-
-
-
-
-
-
-
-
-
4
-
-
-
-
16
~
-
-
-
-
-
ORGANISM
Aspergi l lus f la vus
Aspergi l lus oryzae
Cephalosporium acremonium
Cephalosporium subver t ic i l la tum
Cladosporium re s inae
C ylindr o cephalu m aureum
Fusa r ium caucas icum
Fusa r ium la te r i t ium
Fusa r ium solani
Gliocladium catenulatum
Gliocladium catenulatum
Nocardia sp.
Pénic i l l ium brevicompactum
Pénic i l l ium chrysogenum
Pénic i l l ium c i t r inum
Pénic i l l ium frequentans
Pénic i l l ium l i lacinum
Pénic i l l ium l i lacinum
Pénici l l ium stecki i
Pénic i l l ium sp.
Pycnodothis sp.
Gliocladium catenulatum
Aspergi l lus oryzae
Pénic i l l ium l i lacinum
Cylindrocephalum aureum
CONSTANTS |m.p.° H D
-
-
-
-
-
-
-
-
-
174-176 +194[c]
169-171
170-172
-
- -
-
175-176.5 +194[cl
_
-
-
-
— —
-
1
R E F .
P-726
C-102
H-398
B-67
F-254
S-880
C-97 ; W-1116
C-97
C - 9 7 ; S-949
P-726
M-633
D-172
M-637
C-102
C-102
M-637
M-637
P - 7 2 6 ; S-832
C-102
C-102
K-450
M-633
C-102
M-637
S-880
103
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
^ 1 9 " 2 6 ^ 2
C^HjjgOjjFa
1 C19H2603
NAME OF REACTION PRODUCT
4 -andr ostene -3 ,17 -dione
16,16-di f luoro-17a-hydroxy-4-andros ten-3-one
11α, 1 Iß -dihydroxy - 1 , 4 -androstadien -3 -one
l l ß ,17 j3 -d ihyd roxy- l , 4 -andr os tadien-3-one
TRANSFORMATION
17/3-(20-C=O-21-OH) - 1 7 - C = 0
17/3-(20-C=O-21-OAc)-->17-C = 0
17ß-(20-C=O-21-OPr ) -*17 -C=0
17a-OH-17j3-(20-C=0-21-OH)-> 1 7 - C = 0
1 7 0 - A c - 1 7 - C = O ; Δ4-(5ο-Η)
17ß-(2' -isooctyl) - 1 7 - C = 0 ; 3 /3 -OH-3 - C = 0 ; Δσ->Δ4 17-C=0->17a-OH; 3 / 3 - O H - 3 - C = 0 ; Δ 5 - Δ 4
l i a - O H
l l a - O H ; 17/3-(20-C=O-21-OH) —17/3-OH
1
Δ ; 17j3-Ac->17/3-OH
1
Δ ; 17j3-Ac->17/3-OH; l l a - O H
1
Δ ; 17/3-Ac->17/3-OH
YIELD %
-
-
-
-
-
-
-
-
-
—
-
-
-
-
-
46
59
44
~
—
ORGANISM
Gliocladium catenulatum
Pénic i l l ium nigr icans
Gliocladium del iquescens
Gliocladium luteolum
Gliocladium r o s e u m
Pénici l l ium canescens
Pénic i l l ium char les i i
Pénic i l l ium lividum
Cylindrocephalum aureum
Didymella lycopers ic i
Gliocladium catenulatum
Pénic i l l ium chrysogenum
Pénic i l l ium li lacinum
Pseudomonas chlororaphis
Fusa r ium caucas icum
Nocardia sp.
Flavo bac te r ium dehydrogenans
Sporotr ichum sulfurescens
Spror t r i chum epigaeum
F u s a r i u m javanicum
Septomyxa affinis
Fusa r ium javanicum
Septomyxa affinis
CONSTANTS m.p.° [a]D
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
190-193
174-175
—
183-185
183-185
-
-
-
-
-
-
-
-
-
-
-
-
-
-
- ■
+ 64[d]
- 7[cl
-
- 15[cl
"
REF.
M-633
M-637
M-633
M-633
M-633
M-637
M-637
M-637
S-880
V-1048
M-633
V-1048
M-637
N-648
W-1116
W - l l l l
R-774
M-582
M-582
W-1072
W-1072
F - 2 7 4 ; F-278
W-1072
104
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C 19 H26°3
NAME OF REACTION PRODUCT
11/3,17j3-dihydroxy-1,4-androstadien-3 -one
12a, 17/3-dihydroxy-4,14-andros tadien-3-one
5a-andr o s t a n e - 3 , 6 , 1 7 - t r i o n e
5ß -andros t ane -3 ,6 ,17 - t r ione
5a -andr ostane -3 ,11 ,17 - t r ione
5/3-andr o s t ane -3 ,12 ,17 - t r i one
3 ,17/3-dihydroxy-9,10-seco-1,3, 5 (10) -andros ta t r ien-9-one
3 ,9a -d ihydroxy-9 ,10 - seco -1 ,3 ,5(10)-andros ta t r ien-17-one
3 ? 9/3-dihydroxy-9.10-seco-1,3, 5(10) -andros ta t r ien -17-one
3 9 9ξ -dihydr oxy -9 ,10 - seco -1,3, 5(10)-andros ta t r ien-17-one
TRANSFORMATION
17/3-(20-C=O-21-OH) -17j3-OH
14
12a-OH 4 5
Δ ->Δ ; ketoniz0
6-C = 0 ; 3/3-OH-3-C = 0 ; Δ 5 ->5α-Η
6 - C = 0 ; Δ4~>5α-Η
1 7 ß - A c - 1 7 - C = 0
17/3-Ac->17-C=0
17 |3 -Ac-17 -C=0
9a-OH; Δ 1 ; r ev . aldol. ; enol. ; 1 7 - C = 0 - 1 7 ß - O H
9α-OH; Δ 1 ; rev„ aldoL ; enolc ; 9 - C = 0 — 9 a - O H ; 17j3-OH-*17-C=0
9a-OH; Δ 1 ; r ev . aldol. ; enoL ; 9-C=0->9ß-OH; 17 /3 -OH-17-C = 0 3/3-OH—3-C=0; Δ 5 - > Δ 4 ; Δ 1 ; 9α-OH; rev„ aldol0; enoliz. ; 9 -C=0—9ξ -OH
3a -OH->3-C=0; Δχ»*-(5α-Η); 9a-OH; r ev . a ldo l . ; enoliz. ; 9 - C = 0 - 9 £ - O H
3a -OH—3-C=0 ; Δ1?4-(5/3-Η); 9α-ΟΗ; r ev . aldol. ; enoliz.; 9 - C = 0 - 9 £ - O H
YIELD %
13
< 1
-
7-9
-
-
-
-
-
-
< 1
< 1
7(cr„)
-
-
-
-
-
ORGANISM
Septomyxa affinis
Wojnowicia graminis
Bacil lus pulvifaciens
Bacil lus pulvifaciens
Rhizopus a r r h i z u s
Gliocladium catenulatum
Pénic i l l ium novae zeelandiae
Gliocladium catenulatum
Pénic i l l ium li lacinum
Pénic i l l ium li lacinum
Pseudomonas sp.
Nocardia r e s t r i c t u s
No cardia r e s t r i c t u s
Mycobacter ium fortuitum
Mycobacter ium smegmat i s
Mycobacter ium tuberculos is
Mycobacter ium fortuitum
Mycobacter ium smegmat i s
Mycobacter ium tuberculos is
My cobacter ium fortuitum
Mycobacter ium smegmat i s
CONSTANTS m.p.° [a]D
156
166-168
-
196-196.5
195-196
-
-
-
-
-
133-134
195-197
155-157
-
-
-
—
-
-
+136[c]
-
+79.5[c]
-
-
-
-
-
-
+ 16[c]
+ 48[e]
+ 90[el
-
-
-
-
-
R E F .
S-901
H-381
1-420
T-1027; 1-420
M-604
M-633
M-637
M-633
M-637
M-637
D - 1 7 1 ; M-597
W-1063
W-1063
S-818
S-818
S-818
S-818
S-818
S-818
S-818
S-818
105
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
^19"26^3
NAME OF REACTION PRODUCT
3 , 9 | - d i h y d r o x y - 9 , 1 0 - s e c o -1,3, 5(10) -andros ta t r ien -17-one
17ß-hydroxy-4-andros tene -3,11 -dione
17/3 -hydroxy -4 -androstene -3,16-dione
lö -hydroxy-4-andros tene -3,17-dione
1/3 -hydroxy -4 -androstene -3 ,17-dione
2a-hydroxy-4-andros tene -3,17-dione
2/3 -hydroxy -4 -andros tene -3,17-dione
6/3 -hydroxy -4 -andros tene -3,17-dione
TRANSFORMATION
3a -OH->3-C=0 ; Δι>4(5/3-Η); 9α-ΟΗ; rev . aldol. ; enoliz.; 9 - C = 0 ^ 9 £ - O H
17/3-Ac— 1 7 - C = 0 ; Δ 1 ; 9a -OH; r ev . aldol. ; enoliz.; 9 -C=0->9£-OH
1 7 - C = 0 ^ 1 7 ß - O H
1 7 ß - A c ^ l 7 ß - O H
1 6 - C = 0
1 6 - C = 0 ; 1 7 - C = 0 - 1 7 ß - O H
la -OH
la -OH 3j3-OH-*3-C=0; Δ 5 - Δ 4
Iß-OH
2a-OAc-*2a-OH; 1 7 ß - O A c - 1 7 - C = 0
2ß-OH
2 ß - O A c ^ 2 ß - O H ; 1 7 ß - O A c ^ l 7 - C = 0
6ß-OH
YIELD
% i
< 1
62
-
94
12
-
51
3
12
7
3
10(cr.)
25
1
-
-
-
-
-
ORGANISM
Mycobacter ium tubercu los i s
Mycobacter ium smegmat i s
Saccharomyces ce rev i s iae
Tr ichomonas foetus
Tr ichomonas gallinae
Asperg i l lus oryzae
Neocosmospora vas infecta
Pénic i l l ium notatum
Wojnowicia g ramin i s
Cor t ic ium centrifugum
Pénic i l l ium sp0
Pénic i l l ium sp.
Haplosporel la sp .
Xylar ia sp0
Bacil lus sphaer icus
Nocardia coral l ina
Pénic i l l ium sp.
Baci l lus sphaer icus
Corynebacter ium s implex
Nocardia cora l l ina
Septomyxa affinis
Aspergi l lus niger
F u s a r i u m caucas icum
F u s a r i u m la te r i t ium
CONSTANTS m . p . ° [ e ] p |
177-180
-
-
-
-
182-184
153-155
161-162.5
21505-218
216-218
155-156.5
_
143-145
-
-
-
194-195
-
+182[a]
-
-
-
-
+200[c] +183.5ja]
- 54[c]
- 66[c]
+184[c]
+127.5[c]
+126 [c]
_
- 37[c]
-
-
-
+109
-
R E F .
S-818
S-820
H-385
S-830
S-830; S-829
C-102
S-881
H-336
H-381
D-166
D-163 ; D-167; D-168
D-163 ; D-168
D-165
D-165
H-399
H-399
D-163; D-167; D-168
H-399
H-399
H-399
H-399
F-288
C-97
C-97
106
TABLE I
T ransformat ions by Product
EMPIRICAL FORMULA
C19H2603
NAME OF REACTION PRODUCT
6/3-hydroxy-4-androstene -3,17-dione
6/3 -hydr oxy -4 -androstene -3 ,17-d ione-6a ,7£-H 3
la-hydroxy-4-androstene -3,17-dione
7/3 -hydroxy -4 -androstene -3,17-dione
9a-hydroxy-4-andros tene -3,17-dione
TRANSFORMATION
6/3-OH
3 /3 -OH^3-C=0; Δ 5 - Δ 4 ; 6/3-OH
17/3-Ac->17-C=0
17/3-Ac->17-C=0; 6/3-OH
17/3-(20-C=O-21-OH) - 1 7 - C = 0 ; 6/3-OH
17/3-(20-C=O-21-OAc) ^ 1 7 - C = 0 ; 6/3-OH
17α-ΟΗ-17β-(20-C=0-21-OH) — 1 7 - C = 0 ; 6/3-OH
6/3-OH
la -OH
7β-ΟΗ
9α-OH
9α-OH; 17/3-OH-17-C=0
17/3-Ac->17-C=0
YIELD %
13
4
8(cr0)
-
-
2(cr0)
< 1
-
-
1
-
-
-
-
"
12(cr„)
4
10
< 1
-
10
10
31
17
52
ORGANISM
Fusa r ium solani
Gibberel la saubinett i
Haplosporel la sp.
Rhizopus a r r h i z u s
Rhizopus n igr icans
Rhizopus ref lexus
Wojnowicia graminis
Bacil lus pulvifaciens
Gliocladium catenulatum
Pénici l l ium ci t r inum
Gliocladium catenulatum
Gliocladium catenulatum
Gliocladium del iquescens
Gliocladium luteolum
Gliocladium r o s e u m
Gliocladium catenulatum
Rhizopus a r r h i z u s
Diplodia nata lens is
Neurospora sp.
Haplosporel la sp .
Pseudomonas sp.
Rhizopus stolonifer
Xylar ia sp.
Cylindrocarpon radic icola
Nocardia sp.
Ascochyta linicola
Circinel la muscae
Ar throbac te r sp .
CONSTANTS m . p . ° [of]D
192-19305 +107[cj
183-187
191-194 + 9 9 f c |
-
-
~
194-195 +11505[c]
-
-
190-192 +107[c]
-
-
-
-
~ ~
185-187
255-256.5 +164[c]
225.5-22805
221-225
220.5-222.5 +186
218-223
-
223.5-224.5 +183[c|
218-220
223-224
R E F .
C-97
U-1043
D-165
E-201
E-201
E-201
H-381
T-1027; Ï-420
M-633
M-637
M-633 ; P-726
M-633
M-633
M-633
M-633
M-633
B-32
T-997
T-1037
D-165
D - 1 7 1 ; M-597
T-1037
D-165
S-898; P-740
D-170; D-172; M-597
S-828
R-748
D-172
107
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
^ 1 9 " 2 6 ^ 3
NAME OF REACTION PRODUCT
9a-hydroxy-4-andros tene -3,17-dione
1 la -hydroxy-4 -andros tene -3,17-dione
1 la -hydroxy-4 -andros t ene -3 ,17-d ione-6a ,7£-H 3
1 Iß-hydroxy -4 -andr ostene -3,17-dione
14a-hydroxy-4-andr o s t ene -3,17-dione
15a -hydroxy -4 -andros tene -3,17-dione
TRANSFORMATION
9a-OH; 17j3-Ac-»17-C=0
11a-OH
1 7 ß - A c - 1 7 - C = 0
A 1 6 -17-Ac->17-C=0; l l a - O H
1 7 a - O H - 1 7 ß - A c -1 7 - C = 0
17a-OH-17ß-(20-C = 0 - 2 1 - O H H 1 7 - C = 0
l l a - O H
1 7 ß - O H - 1 7 - C = 0
17a-OH-17ß- (20-- C = 0 - 2 1 - O H H 1 7 - C = 0
14a-OH; 17/3-OH-* 1 7 - C = 0
14a-OH; 3/3-OH—3-C=0;
17ß-Ac->17-C=0
17ß- (20 -C=O-21-OH)->17-C=0
17a-OH-17ß-(20-C = 0 - 2 1 - O H H 1 7 - C = 0
15a-OH
YIELD %
7
< 1
19-23
-
-
20
-
-
-
-
19
-
-
2
4
5-11
-
—
-
-
33-50
ORGANISM
Nocardia r e s t r i c t u s
Pseudomonas sp.
Rhizopus a r r h i z u s
Rhizopus n igr icans
Rhizopus ref lexus
Aspergi l lus oryzae
Pénic i l l ium l i lacinum
Aspergi l lus ochraceus
Pénic i l l ium thomii
Gliocladium catenulatum
Pénic i l l ium l i lacinum
Rhizopus a r r h i z u s
Tr ichomonas gallinae
Pseudomonas ch lororaphis
Wojnowicia g ramin is
Baci l lus pulvifaciens
Pénic i l l ium l i lacinum
Pénic i l l ium l i lacinum
Pénic i l l ium l i lacinum
Fusa r ium caucas icum
Fusa r ium la t e r i t i um
Fusa r ium lini
CONSTANTS m.p.° [α]Ώ
220-222
212-216
226-227
-
-
-
-
-
-
-
216-225
-
—
246-252
260-261.5
252-258
-
~
-
-
190-198
-
-
+162[c]
-
-
-
-
-
-
-
-
-
—
+166[c]
+162[c]
-
-
—
-
-
+217[cl
R E F .
S-885
D - 1 7 1 ; M-597
M - 6 0 1 ; M-604; E-201
M - 6 0 1 ; E-201
E-201
C-102
S-832
V-1048; S-835
M-637
M-637
M-637
B-32
S-829
N-648
H-381
1-420; S-792; T-1027
M-637; E-204
M-637
M-637
C-97
C-97
G-319; T-980
108
TABLE I
T r a n s f o r m a t i o n s by P roduc t
EMPIRICAL FORMULA
Ο , , Η , Α
NAME OF REACTION PRODUCT
15o-hydroxy-4 androstene -3,17-dione
15^-hydroxy-4-andros tene-3,17-dione
16a-hydroxy-4-androstene -3,17-dione
19-hydroxy-4-androstene -3.17-dione
17a -oxa-D-homo-4 -andros tene-3 .17-d ione
TRANSFORMATION
15a-OH
15ö-OH:
17/3-OH >17-C=0
Ι7α-ΟΗ-Ι7β-(20-C=0-21-OH) > 1 7 - C = 0
15,3-OH
16Q-OH
19-OH
17-C=0-> 17a -oxa -17 -C=0
17j3-OH-> 17a -oxa -17 -C=0
17ß-OAc-> 17a -oxa -17 -C=0
YIELD %
~
2
21
-
—
4
-
-
-
25
-
-
-
-
-
-
80
34
-
-
-
-
-
-
ORGANISM
Fusa r ium oxysporum
Fusa r ium solani
Gibberella baccata
Gibberel la saubinetti
Fusa r ium lini
Pseudomonas chlororaphis
Xylar ia sp.
Staurophoma sp.
St reptomyces argenteolus
St reptomyces calii 'ornicus
Streptomyces olivaceus
St reptomyces roseochromogenus
St reptomyces v i r id i s
Cort ic ium mic rosc l e ro t i a
Cephalosporium acremonium
Fusa r ium caucas icum
Fusa r ium la te r i t ium
Fusa r ium solani
Pénic i l l ium l i lacinum
Pénic i l l ium c i t r inum
Pythium ul t imum
Pénic i l l ium l i lacinum
Fusa r ium caucas icum
Fusa r ium la te r i t ium
Fusa r ium solani
Fusa r ium sp.
CONSTANTS m.p.° [a]D
-
-
195-196
-
-
192-197
180-183
185-187
-
-
185-187
-
165
-
-
-
-
211-212
203-208
-
-
-
-
-
—
-
-
-
-
-
+136[c]
+194[c|
-
-
+194[c]
-
+180[c]
-
-
-
-
-
+ 51[c]
-
-
-
-
-
—
R E F .
M-599
C-97
U-1043
U-1043
G-319
N-648
D-165
H-397
F-265
L-491
F-265
F - 2 6 5 ; F - 2 8 8 '
F-265
H-350
H-398
C-97
C-97
C-97
P-737
S-846
S-846
P-737
C-97
C-97
C-97
C-97
109
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
Cl 9H2 e03
NAME O F REACTION PRODUCT
17 a-oxa -D-homo -4 -andro -s t ene-3 ,17-d ione
TRANSFORMATION
1 7 0 - O P r -17a -oxa -17 -C=0
17/3-OFo-17a -oxa -17 -C= 0
17/3-Ac-1 7 a - o x a - 1 7 - C = 0
17a-OH-17/3-Ac— 17a -oxa -17 -C= 0
17/3-(20-C=O-21-OH) —17a-oxa-17-C=0
YIELD %
-
-
-
-
60-65
73
-
-
50
-
-
-
70
-
-
-
-
-
-
-
-
60
-
ORGANISM
Fusa r ium sp .
F u s a r i u m sp.
Aspergi l lus flavipes
Aspergi l lus flavus
Aspergi l lus cheval ier i
Aspergi l lus oryzae
Aspergi l lus oryzae
Aspergi l lus sp.
Cephalosporium ac remonium
Cephalosporium subver t ic i l la tum
Collybia dryophila
F u s a r i u m sp.
Pénic i l l ium adametzi
Pénic i l l ium chrysogenum
Pénic i l l ium c i t r inum
Pénic i l l ium l i lacinum
Pénic i l l ium sp.
Pythium ul t imum
Plutus granular is
Asperg i l lus flavus
Aspergi l lus oryzae
Pénic i l l ium c i t r inum
Pythium ul t imum
Aspergi l lus oryzae
Pénic i l l ium c i t r inum
Pythium ul t imum
Rhizopus suinus
Γ CONSTANTS
π ΐ · Ρ · 0 [<*]ρ|
-
-
207-209
210-212
-
202-206
-
-
-
-
-
-
-
207-209
-
-
-
-
-
-
-
~
-
203-206
-
+ 43[cl
+ 43fc]
-
+ 42|c]
-
-
-
-
~
-
-
+ 43[cl
-
-
-
-
-
-
-
-
—
-
+ 40[c]
R E F .
C-97
C-97
F-270
P-726
C-102
K-461
C-102
C-104
H-398
B-67
S-825
C-97
P-726
F-284
S-846
S-832; P-726
C-99 ; C-102
S-846; S-849
S-825
P-726
C-102
S-846
S-846; S-849
K-461
S-846
S-846; S-849
W-1095
110
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C 1 9 H - 6 0 3
C19H2G°1
NAME OF REACTION PRODUCT
17a-oxa-D-homo-4-andro-s tene-3 ,17-d ione
3/3-hydr oxy -5 - andros tene -7,17-dione
1,3,5(10) - e s t r a t r i ene -3,6/3,17/3-triol 3-methyl ether
13a-hydroxy-13 ,17-seco-1,4 -androstadiene -16 -carboxylic acid
1/3,6 j3-dihydroxy-4-andro-s t e n e - 3 , 17-dione
6/3, 9Ö-d ihydroxy-4-andro-s tene-3 ,17-d ione
6/3,11/3-dihydroxy-4-andro-s tene-3 ,17-d ione
6/3, X-dihydroxy-4-andro -s tene-3 ,17-d ione
9a, 12a -dihydroxy -4 -andro -s tene-3 ,17-d ione
9a, 14a-dihydroxy-4-andro -s tene-3 ,17-d ione
9a, 15/3-dihydroxy-4~andro-s tene-3 ,17-d ione
9a, 18-dihydroxy-4-andro -s tene-3 ,17-d ione
11a, 14a-dihydroxy-4-andro-s tene-3 ,17-d ione
11/3,14a-dihydroxy-4-andro -s tene-3 ,17-d ione
11/3,15a-dihydroxy-4-andro -s tene-3 ,17-d ione
TRANSFORMATION
3/3-OH-3-C = 0 ; Λ 5 -> Δ-i ;
17ß-(20-C=O-21-OAc) ->17a-oxa~17-C = 0
7-C = 0
6/3-OH
17a-oxa-17-C=0-> 17 ,17a-seco-13a-OH-16-COOH
1/3-OH; 6/3-OH
6/3-OH
6/3-OH
6/3-OH
6/3-OH; X-OH; 3/3-OH-»3-C = 0 ; Δ 5 - Δ 4
9a-OH
12a-OH
9a-OH; 12a-OH
9a-OH
14a-OH
9a-OH; 14a-OH
9a-OH
15/3-OH
9a-OH; 15/3-OH
18-OH
9a-OH; 18-OH
11a-OH
11/3-OH
l l ß - O H
YIELD %
35
5
15
-
2
-
t r .
20
t r .
-
-
-
-
-
-
-
-
-
-
-
-
ORGANISM
Aspergi l lus oryzae
Rhizopus spc
Fusa r ium moniliforme
Cephalosporium acremonium
Xylar ia sp.
Pe l l i cu la r i a f i lamentosa
Gibberel la saubinett i
Rhizoctonia solani
Bacil lus pulvifaciens
Cercospora melonis
Cercospora melonis
Cercospora melonis
Cercospora melonis
Cercospora melonis
Pe l l i cu l a r i a f i lamentosa
Cercospora melonis
Cercospora melonis
Cercospora melonis
Cercospora melonis
Cercospora melonis
Cercospora melonis
Pe l l i cu la r ia f i lamentosa
Pe l l i cu la r i a f i lamentosa
Cunninghamella elegans
Pe l l i cu la r i s f i lamentosa
CONSTANTS m.p.° [α]Ό
243-24405
190-192
-
237-239
225-227 [
275-284
271-273
-
253-257
—
243-247
241-244
-
236-238
224-226
-
-
218-220
215-216.5
—
- 83[c]
+ 45[m|
-
+ 68[c]
+ 77 c -m, 1:1]
+132
+ 86 [m]
-
+214[c]
—
+ 137[c]
+139[c]
-
+ 138[c]
+144[d]
-
-
-
+217 c - m , 1:1]
R E F .
K-461
D-175
C-139
H-398
D-165
T-955
U-1043
U-1043
T-1027; S-792
K-473
K-473
K-473
K-473
K-473
T-955
K-473
K-473
K-473
K-473
K-473
K-473
T-955
T-955
U-1043
T-955
I l l
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C19H2604
^19"28^2
NAME OF REACTION PRODUCT
11/3,15a-dihydroxy-4-andro-s tene-3 .17-d ione
2 ß - hy dr oxy -17a - oxa - D -_homo -4 -andros tene -3 ,17-d ione
6j3-hydroxy-17a-oxa-D-homo-4 -andr ostene -3 ,17 -dione
7a-hydroxy-17a-oxa-D-homo-4 -andr ostene -3 ,17 -dione
l l a - h y d r o x y - 1 7 a - o x a - D -homo-4-andr o s t e n e - 3 , 1 7 -dione
16a-hydroxy-17a-oxa-D-homo -4 -andr ostene - 3 , 1 7 -dione
5a -andr ostane -3 ,17 -dione
5/3 -andr ostane -3 ,17 -dione
17/3- hy dr oxy - 3a, 5a -cvc lo-andros tan-6-one
17ß -hydroxy-5a - l - and ro -s ten-3-one
17a-hydroxy-4-andros ten-3-one
17/3-hydroxy-4-androsten-3-one ( testosterone)
TRANSFORMATION
15a-OH
2/3-OH
6/3-OH
7a-OH
17ß-Ac-> 1 7 a - o x a - 1 7 - C = 0
16a, 17a -oxido-17/3 -A c - 1 6 a - O H - 1 7 a -o x a - 1 7 - C = 0
Δ4—5α-Η
d,l - 3 a - O H -d - 3 - C = 0 + l - 3 a - O H
17 /3 -Ac-17-C=0
1 7 / 3 - A c - 1 7 - C = 0 ; 3/3-OAc—3-C=0
Δ4 -5/3-H
Δ ->5ß-H
1 7 ß - A c - 1 7 - C = 0
17 -C=0-17 /3 -OH
1 7 - C = 0 - 1 7 / 3 - O H
3/3-OH—3-C=0; Δ 5 - * Δ 4
17-C=0^17/3-OH
YIELD %
28
5
27
30
—
-
~
-
-
-
-
-
76
-
-
50
83
80
-
-
8.5
ORGANISM
Gibberel la saubinett i
Gnomonia f ragar iae
Pénic i l l ium sp.
Coniothyrium helleborine
Coniothyrium hel leborine
Pénic i l l ium l i lacinum
Cylindrocarpon radic icola
St reptomyces g r i seus
Pseudomonas sp.
Fusa r ium caucas icum
Fusa r ium solani
Fusa r ium caucas icum
F u s a r i u m solani
Bacil lus putr if icus
Clos t r id ium paraput r i f icum
Pénic i l l ium canescens
Saccharomyces ce rev i s i ae
Saccharomyces ce rev i s i ae
Aspergi l lus flavus
Pénic i l l ium notatum
Streptomyces globisporus
St reptomyces v i r idochromogenes
Chlorel la pyrenoidosa
CONSTANTS m . p . " [or]D
221 222
180-182
235-236
275-280
-
_
...
130-132
-
-
-
-
130-131
-
-
182-183
158-159
215-218
-
-
150-152.5
+222|c |
-182 |c |
- 1 3 [ c |
+ 27[c|
-
-
-
+ 109
-
-
-
-
-
-
-
-
- 4 2 l e l
+ 68 |e |
-
-
-
REF.
U-1043
L-496
T-1036
F-282; F -281 ; ! T-994 |
T-994; F-282; ! F-281
S-832
E-195
V-1059
W-1102
V-1056
V-1056; W 1095
V-1056
V-1056
M-545
S-824
M-637
B-81
B-78
H-337
H-337
H-337
H-337
G-321
112
TABLE !
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
C 1 9 H2 8 0 2
NAME OF REACTION PRODUCT
17/3-hydroxy -4 -androsten -3-one ( testosterone)
TRANSFORMATION
1 7 - C = 0 - 1 7 ß - O H
5 4
Δ ->Δ ; 17 -C=0-17 j3 -OH
3 j 3 - O H - 3 - C = 0 ; Δ 5 ^ Δ 4
3/3-OAc—3-C=0; Δ 5 - Δ 4 ; 17-C=0^17/3-OH
17|3-Ac—17j3-OH
YIELD %
~
-
-
60-75
-
-
-
91
41(cr0)
-
-
78
-11
64
-
68
7.5
-
-
-
-
-
-
ORGANISM
Euglena grac i l i s
Fusa r ium sp.
Hydrogenomonas facilis
Pénici l l ium sp.
Rhizobium sp.
Saccharomyces ce rev i s iae
Saccharomyces ce rev i s iae
Saccharomyces fragil is
Tr ichomonas gallinae
Wojnowicia g ramin is
Saccharomyces ce rev i s iae
Acetobacter pas teur ianum
Aspergi l lus flavus
Corynebacter ium sp„
Flavobacter ium carboni l icum
Micrococcus dehydrogenans
Pénic i l l ium notatum
Proac t inomyces ery thropol is
St reptomyces globisporus
St reptomyces vi r idochromogenes
Aspergi l lus oryzae
Cephalospor ium ac remonium
Cladosporium r e s inae
Cylindrocephalum aureum
F u s a r i u m sp.
Neocosmospora vas infecta
CONSTANTS m . p . ° [ûf]D
-
-
-
-
150-151
152-154 +109[e|
-
-
144-147
151
152 +108[el
152-154 +109[e]
-
151
151
-
-
152-154 +109[e]
-
-
-
-
-
-
R E F .
G-322
C-97
F-228
H-336
C-114
M-543; M-550
H-335; H-337
M-572
S-829; S-830
H-381
M-551
K-457
H-337
Z-1133
M-592
E-217
H-337
T-1032
H-335
H-335
C-102
H-398
F-254
S-880
C-97
S-881
113
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
C19H2802
C19H2803
NAME OF REACTION PRODUCT
Tes tos te rone
3/3-hydroxy-5-androsten-17-one
17/3-hydroxy -5a -androstane -3,6-dione
l a -hydroxy - 5a -androstane -3,17-dione
1 l a - hydroxy - 5a -androstane -3,17-dione
11a-hydroxy-5/3-androstane -3,17-dione
9 , 1 0 - s e c o - l , 3 , 5 ( 1 0 ) - a n d r o -s ta t r iene-3 ,9ß ,17 /3- t r io l
l a , 17ß-dihydroxy-4-andro-s ten-3-one
2a, 17ß-dihydroxy-4-andro-s ten-3-one
2/3,17ß-dihydroxy-4-andro-s ten-3-one
TRANSFORMATION
17ß-Ac-17ß-OH
1 7 a - O H - 1 7 ß - A c -17ß-OH
17ß-(20-C=O-21-OH) - 1 7 ß - O H
17/3-(20-C = O - 2 1 -OAc)-»17/3-OH
17ß-(20-C = O - 2 1 -O P r H 1 7 ß - O H
3ß-OAc->3ß-OH
1 7 ß - A c - 1 7 - C = 0
1 7 ß - B u - 1 7 - C = 0
3-C = 0 - A 4 -5 a - H - 3 , 6 - d i - C = 0 ; (via 6/3-OH; Δ4 —► Δ5 ; ketoniz. )
l a -OH
l a - O H ; Δ 4 - 5 α - Η
l l a - O H
l l a - O H
17-C=0—17/3-OH; 9a -OH; Δ 1 ; rev . aldol.; enol. ; 9 - C = 0 -9/3-OH
la -OH
2a-OAc -2a-OH; 17ß-OAc -17/3-OH
2ß-OH
YIELD %
-
62
--
—
-
69
-
-
-
-
-
6
7
1
-
-
t r .
t r .
-
—
ORGANISM
Pénic i l l ium li lacinum
Pénic i l l ium notatum
Pénic i l l ium sp.
Aspergi l lus oryzae
Pénic i l l ium spc
Cylindrocephalum au reum
Neocosmospora vasinfecta
Neocosmospora vasinfecta
C y lindr o c ep halu m au reum
Tr ichomonas gallinae
Fusa r ium caucas icum
Fusa r ium solani
Gliocladium catenulatum
Rhizopus ref lexus
Pénic i l l ium sp.
Pénic i l l ium sp0
Sporotr ichum epigaeum
Sporotr ichum sul furescens
Nocardia r e s t r i c t u s
Pénic i l l ium sp.
Bacil lus sphaer icus
Septomyxa affinis
Gnomonia f ragar iae
CONSTANTS m . p . ° [ a ] D
-
154-155
—
:
-
153.5-155.5
-
-
-
-
-
233-234
211-21305
204-206
-
-
171.5-172.5
239-240
-
-
-
+110[el
-
-
-
+108[c|
-
-
-
-
-
- 9[c]
+110[c]
+114[cl
-
-
+ 19[el
-
-
R E F .
S-832
H-336
H-336; C-102; C-99
C-102
H-336
S-880
S-881
S-881
S-880
S-829
V-1056
V-1056; W-1095
M-633
E-201; M-623
D-163
D-163
M-582
M-582
W-1063
T-1036
H-399
H-399
L-496
114
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
^ 1 9 " 2 8 * ^ 3
NAME OF REACTION PRODUCT
2/3,17ß-dihydroxy-4-andr ei-s ten-3-one
6ß, 17/3-dihydroxy-4-andro-s ten-3-one
9a, 1 7/3- dihydr oxy -4 -andr o-s ten-3-one
1 l o , 17/3 -dihydr oxy -4 -andr o -s ten-3-one
11/3,17/3-dihydr oxy-4-androsten -3-one
12/3,17/3-dihydr oxy-4-andros ten-3-one
14a, 17/3-dihydr oxy-4-andros ten-3-one
TRANSFORMATION
2/3-OAc^2/3-OH; 17/3-OAc-17ß-OH
6/3-OH
9a-OH
9a-OH; 17/3 -Ac — 17j3-OH 11a-OH
17-C = 0 -17 j3 -OH
17/3-Ac^ 17/3-OH
11a-OH; 17/3-Ac—17/3-OH
11a-OH; 17a-OH-17/3-(20-C = 0-21-OH)— 17/3-OH
17-C=0-17 /3 -OH
12/3-OH
1 7 - C = 0 -17/3-OH
14a-OH
YIELD %
-
-
11
-
-
6
3
14
10
-
1
—
-
11
43
90
45
-
-
50
50
86
-
38
ORGANISM
Bacil lus sphaer icus
Corynebacter ium simplex
Septomyxa affinis
F u s a r i u m r o s e u m
Pénic i l l ium sp.
Rhizopus a r r h i z u s
Rhizopus n igr icans
Rhizopus ref lexus
Wojnowicia graminis
Ascochyta linicola
Bac te r ium cyclooxydans
Circ inel la muscae
Nocardia sp0
Aspergi l lus ochraceus
Rhizopus a r r h i z u s
Rhizopus n igr icans
Rhizopus ref lexus
Tr ichomonas gaLlinae
Aspergi l lus oryzae
Pénic i l l ium l i lacinum
Pénic i l l ium notatum
Sporotr ichum epigaeum
Sporotr ichum sulfurescens
Tr ichomonas gallinae
Pénic i l l ium sp.
Saccharomyces ce rev i s iae
Mucor gr iseocyanus
CONSTANTS m . p . ° [o?]D
-
-
212-214
-
-
216-222
205;215-218
196-197
209-211
197-199
—
-
181-181.5
181-181.5
-
-
-
-
178-182
-
121-125°d
117-119
183.5-186
-
-
+ 30[c]
-
-
+ 32[c]
+ 29[c]
+ 79[dl
+103[c]
+104[c'
—
-
+ 93[c]
+ 93[c]
-
-
-
-
+ 90[c]
-
+120[c]
+124[c]
R E F .
H-399
H-399
H-399
R-747
T-1036
E-201
E-201
E-201; M-618
H-381
S-828
S-898; P-740
R-748
D-172
V-1048; S-835
E-201
E-201; M-601
E-201
S-830; S-829
C-102
S-832
H-336
M-582
M-582
S-830; S-829
T-1036
R-749
E-204; M-610
115
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C 1 9 H2 8 0 3
C1 9 H2 8 0 4
NAME OF REACTION PRODUCT
14a, 17ß-dihydroxy-4-andr ei-s ten-3-one
15a, 1 7/3 -dihydr oxy -4 -andr o -s ten-3-one
15/3,17/3-dihydroxy-4-andro-s ten-3-one
16a, 17ß-dihydroxy-4-andro-s ten-3-one
16/3,17/3-dihydroxy-4-andro-s ten-3-one
3ξ, 19-d ihydroxy-4-andro-s ten-17-one
l a , 3ß -d ihyd roxy -5 -and ro -s ten-17-one
3β, 7α-dihydroxy-5-andro-s ten-17-one
3ß, 7/3-dihydr oxy-5-andr o-s ten-17-one
11a, 17/3-dihydr oxy-17a-me thy l -4 -e s t r en -3 -one
l a , 6 ß , 1 7 ß - t r i h y d r o x y - 4 -andros ten-3-one
13a-hydroxy-3-ke to-13 ,17-seco -4 -and ros t ene -16 -car boxy lie acid
TRANSFORMATION
17/3-Ac^ 17/3-OH
15a-OH
15/3-OH
17-C=0->17ß-OH
16a-OH
1 6 a - 0 H ; 1 7 - C = 0 - 1 7 ß - O H
3ß-OH-->3-C = 0 ; Δ 5 - Δ 4
17ß-Ac-17ß-OH
16/3 -OH
16/3-OH; 1 7 - C = 0 - 1 7 ß - O H
19-OH
la -OH
7a-OH
7/3-OH
11a-OH
l a - O H ; 6/3-OH
17a-oxa -17-C=0-+ 13 ,17 - seco -13a -OH-16-COOH
YIELD %
-
8
-
-
4
40(cr.)
-
-
42
-
-
-
-
5
7(cr.)
-
24
-
18
12
-
t r .
-
ORGANISM
Neocosmospora vas infecta
Fusa r ium lini
F u s a r i u m udum
Pénici l l ium ur t icae
Pénic i l l ium sp.
Saccharomyces ce rev i s iae
Pes ta lo t ia funer ea
Streptomyces roseochromogenus
St reptomyces sp.
Wojnowicia graminis
Wojnowicia graminis
Corynebacter ium mediolanum
Streptomyces lavendulae
Streptomyces lavendulae
Wojnowicia graminis
Cort ic ium centrifugum
Hypochnus sasaki i
Pénic i l l ium sp.
Pénic i l l ium sp.
Fusidium sp.
Rhizopus sp„
Rhizopus sp.
Rhizopus n igr icans
Penci l l ium sp.
Aspergi l lus flavipes
Pénic i l l ium sp.
CONSTANTS m . p . ° [α]Ό
-
102-110; 204-206
199-201
199-201
216-218
220-222
183-184
183-184
-
183-187
-
191-192
182-184
183-184
179-182
183.5-185.5
-
288-290
275-277
181.5-183.5
214-216
-
256-260
-
-
+136fm|
+153[c]
+155[c]
+ 67(el
+ 57[e|
+ 76[c]
+ 76
-
+ 63[dl
~
+ 80[c|
+ 66[c]
+ 76
+101[c] + 94[d]
+103[cl
-
+ " M +31.5[e
+ H[c l
- 71[cl
+67.5[c]
-
+ 19[m|
REF.
S-881
T-980; G-319
M-599
M-639
T-1036
H-382
F-266
F-288
S-788
H-381
H-381
A-\
F-271
F-288
H-381
D-166
S-869
D-163; D-168
G-293
D-175
D-175
D-175
M-608
T-1036
H-398
H-398
116
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
ί C1BH,80,
C1 9 H: i 0 O2
^ 1 9 ^ 3 0 ^ 3
C19H30U4
C19n32U2
NAME OF REACTION PRODUCT
13a-hydroxy-3-ke to-13 .17-seco-4-andros tene-16 -carboxylic acid
17/3-hydroxy-5/3-andr ostan -3-one
3a-hydroxy-5a-andros tan -17-one
3/3 -hydroxy -5a -andr ostan -17-one
3a -hydr oxy -5/3 -androstan -17-one
5 -androstene -3 ß, 17ß-diol
1α, 3/3-dihydr oxy -5α -andro -s tan-17-one
3α, l la -d ihydroxy-5/3-andro-stan-17-one
δξ-andros tane-X, 16α, 17/3-t r io l
X, 16α, 17/3-trihydroxy-4-androsten -3-one
5a-andros tane-3a , 17ß-diol
5a-androstane-3/3,17/3-diol
TRANSFORMATION
1 7 - C = 0 - 1 3 , 1 7 -seco-13a-OH-16-COOH
17/3-OH-13,17-s e c o - 1 3 a - O H - 1 6 -COOH
17/3-Ac-13 ,17-seco-13a-OH-16-COOH
Δ -»5/3-H
17/3-Ac-17/3-OH
Δ 4 - 5 α - Η ; 3-C = 0 - 3 a - O H
3-C = 0 - 3 / 3 - O H
Δ 4 - 5 α - Η ; 3-C = 0 -3/3-OH
17a-OH-17/3-(20a-OE-21-H)—17-C = 0
Δ ' - Η ; Δ 4 - 5 / 3 - Η ; 3 - C = 0 - 3 a - O H
17-C=0-17 /3 -OH
1 7 - C = 0 - 1 7 / 3 - O H ; 3ß-OAc-*3/3-OH
l a - O H ; Δ —5a-H; 3-C=0->3ß-OH
17a-OH-17/3-Ac-17-C = 0
16a-OH; Δ 4 - 5 ξ - Η ; 3 - C = 0 - > ?
16a-OH; X-OH
Δ 4 - 5 α - Η ; 3 - C = 0 — 3 a - O H ; 1 7 - C = 0 - 1 7 / 3 - O H
3 - C = 0 - 3 / 3 - O H ; 17 -C=0-17 /3 -OH
YIELD %
2
-
-
-
-
70
-
-
-
-
4
18
86
-
-
1
-
3
-
ORGANISM
Aspergi l lus flavipes
Cephalosporium acremonium
Pénici l l ium li lacinum
Pénici l l ium li lacinum
Aspergi l lus flavipes
Cephalosporium acremonium
Pénici l l ium sp0
Bacil lus putrif icus
Neocosmospora vasinfecta
Euglena grac i l i s
St reptomyces g r i seus
Streptomyces g r i seus
Gliocladium ro seum
Clostr idium paraputr i f icum
Fusidium sp„
Saccharomyces ce rev i s iae
Tr ichomonas foetus
Tr ichomonas gallinae
Tr ichomonas gallinae
Pénic i l l ium sp.
Pénic i l l ium l i lacinum
Wojnowicia graminis
Pes ta lo t ia funerea
Euglena grac i l i s
Saccharomyces ce rev i s iae
CONSTANTS m . p . ° [α]Ό
138.5-139.5
-
-
-
-
139
-
-
-
-
180,5-183
178-179
-
-
-
200-201
-
196-199
279-286
-
163-164
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
+ 93[c]
-
+ 10[d] + 10[c]
-
-
R E F .
H-398
H-398
P-737
P-737
H-398
H-398
H-398
M-545
S-881
G-322
V-1059
V-1059
M-633
S-824
D-175
M-549; M-543
S-830
S-829
S-829
D-163
M-637
H-381
F-266
G-322
V-1046; M-543
117
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
^19"32^2
C^H^OaF
C20 H24°3
1 ^20"24^4
C20H24O5
C 2 0 H 2 5 O 2 F
C20H25O3F
^20 "26^2
NAME OF REACTION PRODUCT
5a-androstane-3/3,17/3-diol
5ß-andros tane-3a , 17/3-diol
5j3-androstane-3a, 17ß-diol
1 la -ethinyl -6a -f luor 0 -l , 3 , 5 ( 1 0 ) - e s t r a t r i e n e -3,17/3-diol
6 a - m e t h y l - l , 4 - a n d r o s t a d i e n e -3 ,11 ,17 - t r ione
1 6 ß - m e t h y l - l , 4 - a n d r o s t a -d i ene -3 ,11 ,17 - t r i one
3-hydroxy-19-nor - l ,3 ,5 (10)~ p regna t r i ene-11 ,20-d ione
3 ,1 la -dihydroxy -19 -nor-1,3,5(10) -pregnat r iene -11,20-dione
3 ,21 -dihydroxy -19 -nor-1 ,3 ,5(10)-pregnat r iene -11,20-dione
3 ,1 la, 21 - tr ihydroxy -19-nor -1,3,5(10) -pregnat r iene -11,20-dione
6a-f luoro-17ß-hydr o x y - H a -rne t hy l -1 ,4 ,9 (11 ) - and ro -s t a t r i en -3 -one
9a -f luor 0 -1 Iß -hy dr oxy -16a -methyl -1 ,4 -andr ostadiene -3,11-dione
2 -methyl -1 ,4 -androstadiene -3,17-dione
16a-methyl-17j3-hydroxy-l , 4 , 9 ( l l ) - a n d r o s t a t r i e n -3-one
17ß-hydroxy-17a-methyl-l , 4 , 9 ( l l ) - a n d r o s t a t r i e n -3-one
TRANSFORMATION
Δ 1 - Η ; 3-C=0-+3ß-OH
Δ ' - Η ; 3 - C = 0 - 3 ß - O H ; 17-C=0->17ß-OH
Δ 5 - 5 α - Η ; 3 - C = 0 - 3 ß - O H ; 17-C=0-»17j3-OH
Δ*—5/3; 3 -C=0-*3a-OH
17-C=0-»17ß-OH
1 Δ j enol.
1 Δ ;
1 7 ß - A c - 1 7 - C = 0 1
Δ
1 Δ ; enol.
1 Δ ; enol.
1 Δ j enol.
1 Δ ; enol.
1 Δ
17-C=0->17ß-OH
Δ (2a-methyl) ; 17/3-OH — 17-C = 0
1 7 - C = 0 - 1 7 ß - O H
1 Δ
YIELD %
6
24
73
-
-
~
9
-
-
43
—
-
-
-
-
-
—
37
ORGANISM
Saccharomyces ce rev i s iae
Saccharomyces ce rev i s iae
Saccharomyces ce rev i s i ae
Clos t r id ium paraput r i f icum
Clost r id ium t e r t ium
Tr ichomonas vaginalis
Septomyxa affinis
Septomyxa affinis
Corynebacter ium s implex
Corynebacter ium hoagii
Corynebacter ium s implex
Corynebacter ium hoagii
Corynebacter ium s implex
Corynebacter ium s implex
Corynebac ter ium s implex
Saccharomyces ce rev i s iae
Bacil lus sphaer icus
Saccharomyces ce rev i s i ae
Bacil lus sphaer icus
Corynebac ter ium s implex
CONSTANTS m . p . ° [o?]D
163
163
163-164
229-230
-
-
—
274-276d
-
-
229-232
~
—
—
"
—
-
172-174
136-139 (solvate)
-
—
+ 4
+ 24[el
-
-
-
+230[c]
-
-
+324[dl
—
-
-
~
-
-
- 46[d
- 52[dl
R E F .
B-80
B-80
M-551
S-823
S-823
S-830
C-93
R-780
R-752
H-386
B-73
H-386
H-386
H-386
G-308
R-752
H-373
R-775
R-775
G-308
118
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C20H26O2
^ 2 θ " 2 6 ^ 2 ^ I2
^ 2 0 " 26^3
C2 0 H2 6 O4
^ 2 0 " 26^5
C 2 0 H 2 7 O 2 F
C^H^OgF
NAME OF REACTION PRODUCT
16 -méthylène -4 -andr ostene -3,17-dione
D-nor-1 ,4 -pr egnadiene -3,20-dione
3 -hydroxy-19-nor - l ,3 ,5 (10) -pr e gnatr ien - 2 0 - one
9a, l l /3-dichloro-17/3-hydroxy -1 la -methyl - 1 , 4 -androstadien-3 -one
17/3-hydroxy-6a-methyl - l ; 4 -androstadiene -3 ,11 -dione
1 l a -hydroxy - 16a - methyl -l , 4 - a n d r o s t a d i e n e - 3 , 1 7 -dione
11/3,17/3-dihydroxy-17a-methy 1 - 1 , 4 , 6 - andr 0 -s t a t r i en-3-one
l , 3 ,5 (10 ) -e s t r a t r i ene -3 ,17 /3 -diol 17-acetate
11a -hydroxy-D-nor -1 ,4 -pr e gnadiene - 3 , 2 0 - dione
3 , l l /3 -d ihydroxy-19-nor -1,3, 5(10) -pre gnatr i en -20-one
3 , l l / 3 ,17a - t r ihydroxy-19-n o r - 1 , 3 , 5(10) -p regna t r i en -20-one
3 , l l j 3 ,21 - t r ihydroxy-19-nor -1,3,5(10) -p regna t r i en-20-one
3 ,7 ,12- t r iketo-5/3-andro-stane-17/3-car boxy lie acid
3 , l l j 3 ,17a ,21- t e t r ahydroxy-1 9 - n o r - l , 3 , 5(10)-pregna-t r i en -20-one
17a, 21 - dihy dr oxy -18 - nor- 4 -pre gnene -3 ,11 ,20 - t r ione
6a -fluoro-17/3 -hydroxy -17a-methyl-l ,4-androstadien-3-one
9a-f luoro- l l /3 ,17ß-dihydroxy-16a-me thy 1-1,4-andr 0 -s tadien-3-one
21 -f luor 0 -11 j3 -hydroxy - 1 9 -nor-4 -pre gnene -3 ,20 -dione
TRANSFORMATION
3/3-OH-*3-C = 0 ; Δ 5 - Δ 4
1
Δ
1
Δ ; enol.
Δ 1
1 Δ ;
17/3-Ac^ 17/3-OH 1
Δ
l l / 3 - O A c - l l / 3 - O H ; 17/3-OAc-17/3-OH
1
Δ ; enol.
l i a - O H
1
Δ ; enoL
1
Δ ; enol.
1
Δ ; enoL
17/3-CH(CH3)CH2-C H 2 C O O H -17j3-COOH
1
Δ ; enol.
21-OH
1
Δ
17-C=0-+ 17/3-OH
l l ß - O H
YIELD %
63
-
62
20
—
26
—
-
59-79
-
—
-
-
t r .
-
-
-
~
ORGANISM
Flavo bacter ium dehydrogenans
Bacil lus sphaer icus
Coryne bacter ium simplex
Streptomyces lavendulae
Corynebacter ium simplex
Septomyxa affinis
Corynebacter ium s implex
Flavobacter ium dehydrogenans
Corynebacter ium simplex
Glomerel la cingulata
Corynebacter ium hoagii
Corynebacter ium hoagii
Corynebacter ium hoagii
P roac t inomyces erythropol is
Corynebacter ium s implex
Colletotr ichum lindemuthianum
Septomyxa affinis
Saccharomyces ce rev i s iae
Curvular ia lunata
CONSTANTS m.p.° [α]Ό
161-162
193-194
238-240
242-244
-
209-210
-
-
218-222
227-230
-
-
-
240
-
-
-
—
-
+110[d]
+164[c]
-
-
+148[cl
-
-
-
+ 7 7 W
-
-
-
-
-
-
—
R E F .
B-76
R-763
B-73
G-317
G-308
R-780
R-752
G-305
K-487
R-763
H-386
H-386
H-386
T-1034
H-386
A-10; A-13
C-93
R-752
R-755
119
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
^ 2 0 " 2 8 ^ 2
C2 0 H2 8 O3
NAME OF REACTION PRODUCT
17 ß - hydroxy-17a-methyl -1,4 -andr ostadien -3 -one
1 -methyl -1 -5a -and ros t ene -3,17-dione
D-nor-4 -pregnene -3 ,20 -dione
1 l a , 17/3 -dihydroxy -1 la -m e t h y l - l , 4 - a n d r o s t a d i e n -3-one
11/3,1 7/3 -dihydroxy -17a-methy l -1 ,4 -andros tad ien -3-one
3 -keto -4 -andr ostene -17/3 -carboxylic acid
17/3-hydroxy~17a-methyl-4-andros tene-3 ,16-d ione
6β-hydroxy-A-nor -3-pregnene-2 ,20-d ione
la -hydr oxy -A -nor-3 -p regnene-2 ,20-d ione
9a - hy dr oxy - A - n o r - 3 -pregnene-2 ,20-d ione
1 l a -hydr oxy -A -nor-3 -p regnene-2 ,20-d ione
TRANSFORMATION
ϊ Δ
M l / 3 - C H 3 ) ; 17/3-OH— 17-C = 0
3/3-OH-*3-C=0; Δ 5 - * Δ 4
l i a - O H
1
Δ
17j3-CH(CH3)CH2-CH2COOH — 17/3-COOH
17j3-CH(CH3)CH2 CH2CH2CH(CH3)2 - 1 7 ß - C O O H
1 6 - C = 0
6ß-OH
7a-OH
9a-OH
11a-OH
YIELD %
21
-
-
-
39
-
-
-
75(cr0)
-
-
-
-
33
_
t r0
tr .
-
6(cr0)
27
44
5
28
ORGANISM
Actinoplanes mi s sou r i ens i s
Baci l lus lentus
Corynebacter ium simplex
Didymella lycopers ic i
Flavobacter ium sp0
Hypomyces solani
Ramula r i a robus ta
Pseudomonas t e s tos t e ron i
Septomyxa affinis
S te reum fasciatum
Volutella ci l iata
Bacil lus sphaer icus
Flavobacter ium dehydrogenans
Sporotr ichum sulfurescens
Bacil lus sphaer icus
Septomyxa affinis
P roac t inomyces erythropol is
P roac t inomyces ery thropol is
Curvular ia lunata
Aspergi l lus nidulans
Cokeromyces r ecu rva tus
Diplodia na ta lens is
Nocardia r e s t r i c t u s
Aspergi l lus nidulans
CONSTANTS m . p . ° [o?]D
-
162-163
-
163-164
-
-
-
164-166
169-171
164-166
-
-
153-155
250-253
262-265
-
245
-
217-219
214-215
161-161.5
227-229
183-184
-
0
-
0|c]
-
-
-
- 3 | c |
0 | c |
0[c|
-
-
+ 209|c]
- 33[c]
+ 40|cl
-
-
-
+ 24|c]
+ 65 | c |
+ 94|cl
+ 93|c]
REF .
M-536
R-750
N-665; N-667a
V-1052; W-1096
1-430
L-525
L-525
L-508
W-1072; E-205
T-959
L-525
H-373
R-763
E-205; M-582
G-305
E-206
T-1034
T-1034
S-950
T-1006; W-1076
L-503a
W-1078; L-502
W-1079
W-1076; T-1006
120
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
| C2 0 H2 8 O3
C 2 0 H2 8 O4
^ 2 0 " 2 8 ^ 5
C 2 0 H 2 9 O 2 C 1
C 2 0H 3 0O 2
C 2 0H 3 0O 2 S
^ 2 0 " 3 0 ^ 3
NAME OF REACTION PRODUCT
16a -hydroxy -A -nor-3 -pregnene-2 ,20-dione
21 -hydr oxy -A -nor- 3 -pregnene-2 ,20-dione
9a-hydroxy-19-nor-4 -pregnene-3 ,20-dione
l l a - h y d r o x y - 1 9 - n o r - 4 -pregnene-3 ,20-d ione
l l /3-hydroxy-19-nor-4-pregnene-3 ,20-d ione
14a-hydroxy-19-nor -4-pregnene-3 ,20-d ione
21-hydroxy-19-nor-4-pregnene-3 ,20-d ione
11/3,17a-dihydroxy-19-nor-4-pregnene-3 ,20-d ione
X-hydroxy-3-ke to -4 -andro-stene-17/3 -car boxy lie acid
I4 ,17/3-dihydroxy-4-es t ren-3-one 17-acetate
l l / 3 ,17a ,21- t r ihydroxy-18-nor -4-pregnene-3 ,20-d ione
3/3-chloro-16a-hydroxy-19-nor-5-pregnen-20-one
17/3-hydroxy-17a-methyl- l -5α -andr osten -3 -one
17/3-hydroxy -1 la -methyl-4 -andros ten-3-one
17a-methylsul f inyl-4-andro-s ten-3-one ( s t e reochemis t ry at S uncertain)
17a - methylsulf iny 1-4-andr 0-s ten-3-one (opposite s t e reochemis t ry at S from preceding compound)
6/3,17/3-dihydr oxy -4 -methyl -4-andr osten -3-one
la, 17/3-dihydr oxy-4 -methyl -4 -andros ten-3-one
7/3,17ß-dihy dr oxy-4-methyl -4 -andr osten -3 -one
J-Λ J
TRANSFORMATION
16a-OH
21-OH
9a-OH
l l a - O H
11/3-OH
14a-OH
21-OH
d l - d - 2 1 - O H + 1
11/3-OH
17j3-CH(CH3)-CH2CH2COOH -17ß-COOH; 3/3-OH-3-C = 0 ; Δ 5 - Δ 4 ; Χ-ΟΗ
1ξ-ΟΗ
21-OH
16a-OH
1 Δ
3 /3-OH-+3-C=0; Δ 5 - Δ 4
17a-SCH3-> 17a-S(0)CH3
17a-SCH 3 ^ 17a-S(0)CH3
6/3-OH
7a-OH
7/3-OH
YIELD %
59
25
-
66
20
15
46
-
-
1
25
-
-
-
-
-
tr0
2
12
ORGANISM
Streptomyces roseochromogenus
Aspergi l lus niger
Cylindrocarpon radic icola
Rhizopus n igr icans
Curvular ia lunata
Helicostylum pi r i forme
Aspergi l lus niger
Ophiobolus herpot r ichus
Curvular ia lunata
Streptomyces gelat icus
Corynebacter ium s implex
Colletotr ichum linde muthianum
Streptomyces roseochromogenus
Actinoplanes mis sour i ens i s
Corynebacter ium helvolum
Rhizopus stolonifer
Rhizopus stolonifer
Rhizopus n igr icans
Rhizopus n igr icans
Rhizopus n igr icans
CONSTANTS m . p . ° [ot]D
213-214
148-149
-
171-173
215-217
202-204
—
-
-
255-258d
149-151
-
-
-
-
—
218-220
190-192
189-190.5
+ 32[c]
+ 76[c]
-
+ 62[cl
+158[c]
+166[c]
-
-
-
-
-
-
-
-
—
+ 10[c]
+105[d]
+106[c]
R E F .
L-506; L-502
W-1077; L-502
S-898; P-740
B-73; C-117
B-73
B-73
Z-1124; Z-1123; R-783
W-1102
R-773
H-364
K-487
A-12
Z-1128
M-536
M-546
D-174
D-174
K-445
K-445
K-445
121
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
^20'"30*-'3
C 2 0H 3 0O 3 S
C 2 0 H 3 0 O 4 S
1 ^ 20^32^3
1 ^ 2 l "22^3
NAME OF REACTION PRODUCT
11a, 17ß-dihydroxy -4 -methyl -4 -andros ten-3-one
l a , 17/3 -dihydr oxy -17a -methy l -4 -andros ten-3-one
2/3,17/3-dihydroxy-17a-methy l -4 -andros ten-3-one
6/3,17/3-dihydroxy-17a-methy l -4 -andros ten-3 -one
9a, 17/3-dihydr oxy-17a-methyl -4 -an dr osten -3 -one
11a, 17ß-dihydroxy-17a-methyl -4 -androsten -3 -one
16/3,17/3-dihydr o x y - H a -rne thy l -4 -andros ten-3-one
17/3- hydr oxy -7a -methyl -su l f inyl -4-andros ten-3-one
1 la -hydr oxy -17a -methyl -sulf inyl -4 -androsten -3 -one ( s te reochemis t ry at S unknown)
1 la-hydroxy-17/3-methyl -su l f inyl -4-andros ten-3-one ( s t e reochemis t ry at S unknown)
l la -hydroxy-17/3-methyl -sulf iny 1 -4 -andros ten -3 -one (opposite s t e r eochemis t ry at S from preceding compound)
11a-hydr oxy-17/3-methyl-su l fonyl -4-andros ten-3-one
3/3,16a-dihydroxy-19-nor-5a-pregnan-20-one
17a-ethinyl-17/3-hydr oxy-1 ,4 ,6 -andros t a t r i ene -3,11-dione
TRANSFORMATION
l l a - O H
3j3-OH-3-C = 0 ·
2/3-OH
6/3-OH
9a-OH
l l a - O H
16/3-OH
7a-SCH3—7a-S(0)CH3 17/3-OAc-17/3-OH
l l a - O H ; 1 7 a - S C H 3 -17a-S(0)CH3
l l a - O H
l l a - O H ;
l l a - O H
16a-OH
Δ*
YIELD %
7.5
-
-
90
4
-16
47
-
49-70
-
29
-
-
-
ORGANISM
Rhizopus n igr icans
Pénic i l l ium sp.
Gnomonia f ragar iae
Gibberella saubinetti
Rhizopus a r r h i z u s
Rhizopus n igr icans
Rhizopus ref lexus
Ascochyta linicola
Rhizopus a r r h i z u s
Rhizopus n igr icans
Rhizopus ref lexus
Sporotr ichum sul furescens
Curvular ia lunata
Calonectr ia decora
Rhizopus stolonifer
Rhizopus stolonifer
Rhizopus stolonifer
Rhizopus stolonifer
S t reptomyces roseochromogenus
St reptomyces sp„
Bacil lus sphaer icus
CONSTANTS m . p . ° [α]Ό
179.5-180.5
-
-
-
252-253
-
190-191
160-161.5
-
154-156
-
189.5-190
225-226
223-224
297-299d
267-268
-
-
+ 7 2 [ c |
-
-
-
+ 3|c]
-
-
+ 66[c] + 59[e|
-
-
-
+ l l [m]
- 88[c]
+105
-
-
REF.
K-445
G-293
L-496
U-1043
E-201
E-201; M-613
E-201
S-828
E-201
E-201; M-608
E-201
M-582
S-950
H-405
D-174; D-176
D-176
D-176
D-176
W-1093
W-1093
G-304
122
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C21H2306C1
C21H2306F
C21H2402C12F2
^ 21 ** 24 ®2 ̂ ^2 ■*■ ^
C^iH^C^FI
* " 2 l " 2 4 ^ 3
C 2 1 H2 4 0 4
C 2 1 H 2 4 0 5
C 2 1 H 2 4 0 5 F 2
^ 2 1 ^ 2 4 ^ 6
C21H2406C1F
C2iH2502F
C21H2503Br
NAME OF REACTION PRODUCT
9a-chloro -14α,17α,21-t r ihydroxy-1 ,4 ,6 -p regna-t r iene-3 , 11,20-trione
9a-fluoro-14α, 17α, 21-t r ihydroxy-1 ,4 ,6 -p regna-t r iene-3 , 11,20-trione
9a, l l /3-dichloro-6a,21-dif luor o -1,4 -pr egnadiene -3,20-dione
9a, l l /3-dichloro-6a-fluoro-21- iodo- l ,4-pregnadiene-3,20-dione
6a- f luoro-21- iodo- l ,4 ,9 ( l l ) -p regna t r iene-3 ,20-d ione
17a-ethinyl-17/3-hydroxy-1,4 -andr ostadiene -3,11 -dione
17a-ethinyl-11/3,17/3-dihydroxy-l , 4 , 6 - a n d r o s t a t r i e n - 3 - o n e
l l /3-hydroxy-3,20-diketo-l ,4-pregnadien-18-oic acid (18 41) lactone
17a, 21-dihydroxy-1,4,6-pregnat r iene-3 ,11 ,20- t r ione
6,9a-difluor0-11/3,17a, 21-t r ihydroxy-1 ,4 ,6 -p regna-t r i ene -3 ,20-d ione
9α, 17α, 21- t r ihydroxy-1 ,4 ,6-pregnat r iene-3 ,11 ,20- t r ione
14α, 17α, 21- t r ihydroxy-1 ,4 ,6-pregnat r iene-3 ,11 ,20- t r ione
12a-chloro-6a-fluoro-16a, 17a, 21-trihydroxy-1,4-pregnadiene-3,11, 20-tr ione
17a -ethinyl -6a -fluor 0-17/3-hydroxy -1,4 -andr ostadien -3-one
6/3-fluoro-l, 4,9(11) -pregna-t r i ene-3 ,20-d ione
21-f luoro- l ,4 ,9( l l ) -pregna-t r iene -3 ,20 -dione
9a -b romo-1 ,4 -p r egnadiene -3,11,20-trione
TRANSFORMATION
14a-OH
14a-OH
1
Δ
Δ1
Δ1
Δ1
Δ1
11/3 -OAc^ll/3-OH; 17/3-OAc-17/3-OH
Δΐ
Δ1
2 1 - O A c - 2 1 - O H ; Δ1
Δ1
9a-OH
14a-OH
Δ1
Δ1
Δ1
Δ1
1
Δ
YIELD %
—
—
—
—
-
—
-
75
—
-
-
—
—
-
—
ORGANISM
Curvular ia lunata
Curvular ia lunata
Corynebacter ium simplex
Corynebacter ium simplex
Corynebacter ium simplex
Bacillus sphaer icus
Bacil lus sphaer icus
Fla vo bac ter ium dehydrogenans
Corynebacter ium simplex
Bacil lus sphaer icus
Eaci l lus sphaer icus
Corynebacter ium simplex
Helicostylum pir i forme
Helicostylum pi r i forme
Nocardia aurant ia
Septomyxa affinis
Corynebacter ium simplex
Corynebacter ium simplex
Corynebacter ium hoagii
CONSTANTS m.p.° [a]D
— —
— —
— —
— —
- —
— —
- -
194-195 —
225° d +246|d] 235°d (polymorph)
— —
- -
- -
— —
— —
- -
— —
R E F .
G-302
G-302
R-758
R-758
R-758
G-304
G-304
G-304
U-1044
G-310
G-310
A-7
G-302
G-302
F-261
C-93
R-757
R-773
H-379
123
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C21H2503C1
C21H2503C12F
C21H2503C12I
C 2 1 H 2 5 ° 3 F
C 2 l H 2 5 0 3 I
C21H2503C12I
C21H2504F
C21H2504FS
1 ^2l"25^4-' : ,3
C21H2505Br
C21H2505C1
NAME OF REACTION PRODUCT
9a-ch lo ro -1 ,4 -p r egnadiene -3,11,20-trione
9a, 11/3-die hlor 0-21-fluor o-17α-hydroxy-1,4-pregna-diene-3 ,20-dione
9a,l l /3-dichloro-170-hydroxy-21- iodo- l ,4 -pregnadiene-3 , 20-dione
17a-ethinyl-9a-f luoro-l l /3 , 17/3-dihydroxy-l,4-androstadien-3 -one
6a - f luo ro - l ,4 -p regnad iene -3,11,20-tr ione
6/3-f luoro-l ,4-pregnadiene-3,11,20-tr ione
9a -fluoro-1,4 -pr egnadiene -3,11,20-tr ione
6a -fluor o -17a -hydroxy -1,4,9(11) -p regna t r i ene -3,20-dione
17a-hydroxy-21-iodo-l ,4 ,9( l l ) -pr e gnatr iene - 3 ,2 0 - dione
9a, 11/3-die h loro- 17a -hydroxy -21-iodo-1,4-pr egnadiene-3,20-dione
9a -fluoro -17a -hydroxy -1,4 -pregnadiene-3 ,11,20- t r ione
9a - f luoro -21-hydroxy- l ,4 -pr egnadiene-3,11,20-t r ione
12a-f luoro-21-hydroxy- l ,4-pr egnadiene-3,11,20-tr ione
9a-f luoro-17a-hydroxy-21-mer capto -1,4 -p regna-d i ene -3 , 11,20-trione
6α, 9α, 21-trifluor 0-11/3,17a-dihydroxy-1 ,4-pregna-d iene -3 , 20 -dione
9a-bromo-17a,21-dihydroxy-1,4 -pregnadiene-3,11,20-tr ione
9a-bromo-17a, 21-dihydroxy-1,5-pregnadiene-3,11,20-tr ione
9a-chloro-17a,21-dihydroxy-1,4 -pregnadiene -3,11,20 -t r ione
TRANSFORMATION
1 Δ
Δ1
Δ1
Δ1
Δ1
Δ1
1 Δ
Δ1
1 Δ
Δ1
Δ1
Δ1
A1; 21 -OAc-21-OH
21-SAc ->21-SH
1 Δ
1 Δ
21-OAc-^21-OH
1 Δ
YIELD %
-
—
—
—
-
-
-
—
—
-
-
-
-
—
—
—
—
ORGANISM
Corynebacter ium hoagii
Corynebacter ium s implex
Corynebacter ium s implex
Bacil lus sphaer icus
Septomyxa affinis
Septomyxa affinis
Corynebacter ium simplex
Corynebacter ium simplex
Corynebacter ium simplex
Corynebacter ium s implex
Corynebacter ium simplex
Corynebacter ium simplex
Bacillus sphaer icus
Flavobacter ium dehydrogenans
Septomyxa affinis
Corynebacter ium s implex
Flavobacter ium dehydrogenans
Corynebacter ium s implex
CONSTANTS m.p.° [a]D
- -
— —
— —
— —
- -
- -
- -
— —
- -
- -
- -
- -
- -
— —
267-272 —
— —
— —
REF.
H-379
R-756 j
R-756 !
N-667
C-91
C-91
H-379
H-391
R-756
R-756
H-379
N-668
W-1083
N-685
M-534
N-668
N-690
N-668
124
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C21H2505C1
C21H2505F
C21H2505N
C21H2506Br
C21ri26U2
C21H2602BrCl
C 2 1 H a 0 2 B r F
C21H2602Br2
C ^ O . C I F
NAME OF REACTION PRODUCT
9a-chloro-17a, 21-dihydroxy-1, 5-pregnadiene-3? 11,20-tr ione
2-fluor o-17a, 21-dihydroxy-1,4 -pr egnadiene -3,11,20-tr ione
9a-fluoro-17a, 21-dihydroxy-1,4 -pr egnadiene -3,11,20-tr ione
9a-fluoro-17a, 21-dihydroxy-1, 5-pregnadiene-3,11,20-tr ione
21-hydroxy-17ß, 20a-oxido-16-oximino-1,4-pr egna-diene-3,11-dione
9a-bromo-l l /3,14a,17a,21-t e t r a h y d r o x y - l , 4 , 6 - p r e g n a -t r i ene-3 ,20-d ione
9a - f l uo ro -6£ , I7a ,21 -t r ihydroxy -1,4 -pregnadiene -3,11,20-trione
9a-f luoro-14a ,17a ,21-t r ihydroxy- l ,4 -p regnad iene -3,11,20-trione
9a-fluor0-11/3,14α, 17α, 21-t e t r a h y d r o x y - l , 4 , 6 - p r e g n a -t r iene -3 ,20 -dione
9α-fluor 0-11/3,16α, 17α, 21-t e t r a h y d r o x y - l , 4 , 6 - p r e g n a -t r iene-3 ,20-dione
17a-ethinyl-17j3-hydroxy-1,4 -andros tadien-3 -one
1 ,4 ,9 ( l l ) -p regna t r i ene -3,20-dione
1,4, l l - p r e g n a t r i e n e - 3 , 2 0 -dione
1,4,16 -pregnatr iene - 3 , 2 0 -dione
9a-bromo- l l /3 -ch loro- l ,4 -pr egnadiene-3,20-dione
9a-bromo-l l /3- f luoro- l ,4-pr egnadiene-3,20-dione
9a, 11/3-dibromo-l,4 -pr egna-diene-3 ,20-dione
9a -ch lo ro - l l ß - f luo ro - l , 4 -pr egnadiene -3 ,20 -dione
TRANSFORMATION
21-OAc-21-OH
Al(2aF)
1
Δ
21-OAc-21-OH
1
Δ
14a-OH
6 | -OAc-βξ -OH; 21-OAc->21-OH
14a-OH
14a-OH
16a-OAc^l6a-OH; 21-OAc^21-OH
Δ1
Δ1
Δ1
1
Δ
Δ1
1
Δ
1
Δ
1
Δ
YIELD %
—
23
39
—
—
—
—
—
—
—
-
-
-
—
-
—
—
ORGANISM
Flavobacter ium dehydrogenans
Nocardia coral l ina
Corynebacter ium simplex
Flavobacter ium dehydrogenans
Bacil lus sphaer icus
Curvular ia lunata
Flavobacter ium dehydrogenans
Helicostylum pir i forme
Curvular ia lunata
Flavobacter ium dehydrogenans
Corynebacter ium simplex
Corynebacter ium s implex
Didymella lycopers ic i
Corynebacter ium simplex
Corynebacter ium simplex
Corynebacter ium simplex
Corynebacter ium simplex
Corynebacter ium s implex
CONSTANTS m.p.° [a]D
_ _
232-236 +145[m]
— —
— —
— —
— —
— —
— —
—
— —
135-138; +75[c] 147-150
166-168 +112[a]
— —
— —
— —
— —
R E F .
N-690
H-402; H-401
N - 6 6 8 ; N-669
N-690
N-686
G-302
G-309
N-669
G-302
G-299
N-665
R - 7 7 3 ; R-754
V-1052; W-1096
H-388; O-700
R-754
R-754
R-754
R-754
125
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C21H260,C1I
C ^ H ^ C l ,
C^H^O.FI
C21 H26°3
1 ^ 21 " 26^4
NAME OF REACTION PRODUCT
9a - iodo - l l / 3 - ch lo ro - l , 4 -pr egnadiene -3 ,20 -dione
9 a , l l / 3 - d i c h l o r o - l , 4 - p r e g n a -diene-3 ,20-dione
9a -iodo -11/3- fluor o - 1 , 4 -pr egnadiene -3 ,20 -dione
17a-e th iny l - l lß ,17 /3-d ihydroxy-1 ,4 -andros t a -dien-3-one
17a-ethinyl-11/3,17/3-d ihydroxy-4 ,6-andros ta -dien-3-one
1 ,4 -p regnad iene -3 ,11 ,20 -tr ione
21 -hyd roxy -1 ,4 ,6 -p r egna -t r i ene -3 ,20-d ione
1 7 a - h y d r o x y - l , 4 , 9 ( l l ) -p re gnatr iene -3 ,20 -dione
2 1 - h y d r o x y - l , 4 , 9 ( l l ) -p regna t r i ene -3 ,20-d ione
11a -hydroxy-1 ,4 ,16 -p regna -t r i ene -3 ,20-d ione
l l / 3 - h y d r o x y - l , 4 , 1 6 - p r e g n a -t r i ene-3 ,20-d ione
21 -hydroxy-1 ,4 ,16 -p regna -t r i ene -3 ,20 -d ione
21-hydroxy- l l /3 , 12/3-oxido-1,4 -pr egnadiene - 3 , 2 0 -dione
1 la -hydroxy-16û ,1 la -ox ido -1,4 -pregnadiene - 3 , 2 0 -dione
21-hydroxy-16α,17α-oxido-1,4 -pregnadiene - 3 , 2 0 -dione
21-hydroxy-1 ,4-pregnadiene -3 ,11 ,20 - t r ione
17a,20a-dihydroxy-9j3,11/3-o x i d o - 1 , 4 , 6 - p r e g n a t r i e n -3-one
TRANSFORMATION
Δ1
l
Δ
1
Δ
1
Δ
ll/3,17ß-diOAc-> 11/3,17/3-diOH
1
Δ
1
Δ
1 Δ ;
21-OAc-21 -OH 1
Δ
i
Δ
11a-OH
11/3-OH
2 1 - O A c - 2 1 - O H ; 3/3-OAc->3-C = 0 ; Δ 5 ^ Δ 4 ; Δ '
21-OH
1
Δ
3 /3 -OH^3-C=0 · Δ 5 - ^ Δ 4 ; Δ1
1
Δ
20-C=O->20a-OH
YIELD %
-
-
-
—
—
71
30
-
~
-
-
~
—
—
-
—
—
-
ORGANISM
Corynebacter ium simplex
Corynebacter ium simplex
Corynebacter ium simplex
Bacil lus sphaer icus
Flavobacter ium dehydrogenans
Actinoplanes mi s sou r i ens i s
Septomyxa affinis
Didymella lycopers ic i
Corynebacter ium simplex
Corynebacter ium s implex
Rhizopus n igr icans
Curvular ia lunata
Corynebacter ium s implex
Wojnowicia graminis
Bac te r ium mycoides
Bac te r ium havaniensis
Bacil lus lentus
Bacil lus sphaer icus
Calonectr ia decora
Corynebacter ium s implex
Rhodotorulla longiss ima
CONSTANTS m . p . ° [ a ] D
-
198-208d
-
—
-
156-159
179-181
166-168
233-235
-
-
-
—
—
-
206-208
220-222d
-
-
+ 184[c]
-
—
—
-
+224[cl
+112[a]
- 19[c]
-
-
-
—
—
-
+ 88[dl
—
-
R E F .
R-754
R-754
R-754
G-304
G-304
M-536
E-208; W-1072
W-1096; V-1052
R-773
R-755
H-388; O-700
H-388; O-700
H-388; O-700
D-157
F-240
F-233
R-750
S-942
W-1096
N-665
G-303
126
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
^ 2 1 " 2 6 ^ 4
C^H^aABrCl
C2 1H2 604BrF
C 2 1 H 2 6 0 4 B r2
C21H2604C1F
C21H2604C1I
C 2 1 H 2 6 0 4 C 12
C21H2604FI
^ 2 l " 2 6 ^ 4 ^ 2
C21H2604S
NAME OF REACTION PRODUCT
17a, 20/3-dihydroxy-9/3,11/3-ox ido-1 ,4 ,6 -pr egnatr ien -3-one
1 1 a , 2 1 - d i h y d r o x y - l , 4 , 1 6 -pregna t r iene-3 ,20-d ione
11/3,21-dihydroxy-l , 4 , 1 6 -pregna t r iene-3 ,20-d ione
l - l l /3 -hydroxy-3 ,20-d ike to-4-pregnen-18-oic acid (18^11) lactone
9a -b romo- l l /3 -ch lo ro -17a , 21 -d ihyd roxy- l , 5 -p regna -diene-3 ,20-dione
9a -ch loro- l l /3 -bromo -17a, 21-d ihydroxy- l , 5 -pregnadiene-3,20-dione
9 a - b r o m o - l l ß - f l u o r o - 1 7 a , 2 1 -dihydr oxy - 1 , 5 -pr egnadiene -3,20-dione
9a- f luoro- l l /3 -bromo-17a , 2 1 -d ihydroxy- l , 5-pr egnadiene -3,20-dione
9 a , l l / 3 - d i b r o m o - 1 7 a , 2 1 -dihydr oxy - 1 , 5 -pr egnadiene -3,20-dione
9a-chloro- l l /3- f luoro-17a , 2 1 -d ihydroxy- l , 5-pr egnadiene-3,20-dione
9a - f luo ro - l l / 3 -ch lo ro -17a ,21 -dihydroxy -1 ,5 -pr egnadiene -3,20-dione
9a - iodo - l l / 3 - ch lo ro -17a ,21 -dihydr oxy -1 ,5 -pr egnadiene -3,20-dione
9 a , l l / 3 - d i c h l o r o - 1 7 a , 2 1 -dihydr oxy -1 ,5 -p re gnadiene -3,20-dione
9a- iodo-l l /3-f luoro-17a, 2 1 -d ihydroxy- l , 5-pre gnadiene-3,20-dione
9a , l l / 3 -d i f luo ro -17a ,21-dihydroxy-1,5-pregnadiene -3,20-dione
6a ,9a-di f luoro-15a-hydroxy-4 -pr egnene -3 ,11 ,20 - t r ione
17a - hydroxy - 21 - me r capto -1,4 -pr egnadiene - 3 , 1 1 , 2 0 -tr ione
TRANSFORMATION
20-C=O-20/3-OH
21-OH
21-OH
d l - 2 1 - H -d-21-OH + l -21-H
21-OAc-21-OH
21-OAc^21-OH
21-OAc-21-OH
21-OAc 21-OH
21-OAc -21 -OH
21-OAc-21-OH
21-OAC-21-OH
21-OAc - 2 1 - O H
21-OAc-21-OH
21-OAc-21-OH
21-OAC-21-OH
15a-OH
21-SAC-21-SH
YIELD %
-
-
-
—
—
—
—
—
—
—
—
—
—
-
~~
-
ORGANISM
Coryne bacter ium simplex
Ophiobolus herpot r ichus
Ophiobolus herpot r ichus
Ophiobolus herpot r ichus
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Flavobacter iu m dehydrogenans
Pénic i l l ium ur t icae
Flavobacter ium dehydrogenans
CONSTANTS m.p.° [α]Ό
-
-
-
-154
— —
— —
— —
- —
— —
— —
— —
- —
— ~
— —
~ ~
-
R E F .
G-303
O-700; H-388
O-700; H-388
V-1055
N-691
N-691
N-691
N-691
N-691
N-691
N-691
N-691
N-691
N-691
N-691
A-31
N-685
127
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL i FORMULA
^ 2 1 " 2 6 ^ 5
NAME OF REACTION PRODUCT
l l /3 ,21-dihydroxy-3,20-diketo -1,4 -pr egnadien -18 -a l ( 1 8 - * l l ) hemiaceta l
17a, 21-dihydroxy-9/3,11/3-ox ido- l ,4 -p regnad iene-3,20-dione
16o, 21-dihydroxy-11/3,12/3-ox ido- l ,4 -p regnad iene-3,20-dione
17a,21-dihydroxy-1,4-pregnadiene-3,11, 20-t r ione (prednisone)
TRANSFORMATION
Δ1
d , l - d - A I + 1
21-OAC-21-OH
16α-ΟΗ
Δ1
YIELD %
—
—
-
—
:
62
-
-
—
-
—
58-85 (cr.)
90
—
64
-
-
72(cr.)
-
-
—
—
—
ORGANISM
Calonectr ia decora
Didymella lycopers ic i
Didymella lycopers ic i
St reptomyces roseochromogenus
Bacillus lentus
Bacillus pulvifaciens
Bacillus sp.
Bacil lus sphaer icus
Bacil lus subti l is
Bacter ium cyclooxydans
Calonectr ia decora
Calonectr ia decora
Corynebacter ium simplex
Didymella lycopers ic i
Didymella lycopers ic i
Fusa r ium oxysporum
Fusa r ium solani
Fusa r ium solani
Gliocladium r o s e u m
Gloeosporium ol ivarum
Graphiola cyl indrica
Helminthospor ium gramineum
Helminthospor ium tu rc icum
Helminthospor ium zizaniae
CONSTANTS m . p . ° [ a ] D
—
-
—
—
224-225
225-230
-
232-233
-
231-234
-
233-235d
231-234
226-232
229-231d
231-234
229-233
230-234
229-233
-
—
-
—
-
-
—
—
+170[d|
+164[m]
-
+166[d]
-
+169fd]
-
+172[d|
-
—
-
+169[d]
+170[d]
+164[cl
+171[dl
-
-
-
—
REF.
W-1096
V-1055; #-1102
W-1096
D-157
R-750
1-420
S-848
S-942
L-521
K-480
V-1053; W-1096
S-951
N-671; N-665; H-389; H-387
W-1096
V-1052
C-125
V-10 53
K-462
S-857
K-465
K-465
K-465
S-857
K-465
128
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
^ 2 1 " 2 6 ^ 5
NAME OF REACTION PRODUCT
prednisone
TRANSFORMATION
Δ1
α , Ι - α - Δ ^ 1
21-OAc->21-OH
21-OH
Δ1'4 (5α-Η)
Δ Μ ( 5 β - Η )
Δ ^ δ / Β - Η ) . 21-OAc->21-OH
3 û - O H - 3 - C = 0 ; Δ 1 ' 4 (5/3-H)
YIELD %
-
—
—
-
75-81
-
-
—
-
-
3
52
-
-
-
—
-
-
-
-
-
-
-
—
ORGANISM
Hypomyces solani
Micromonospora chalcea
Mycobacterium f la vu m
Mycobacterium smegmat i s
Mycobacter ium sp.
Nocardia coral l ina
Ophiobolus he te ros t ropus
Pro taminobac te r alboflavum
Pro taminobac te r rub rum
Septomyxa affinis
Septomyxa affinis
Streptomyces olivochromogenus
Didymella lycopers ic i
Bacil lus megater ium
Colletotr ichum linde muthianum
Ophiobolus herpot r ichus
Sclerot inia fructicola
Calonectr ia decora
Didymella lycopers ic i
Nocardia blackwelli
P ro taminobac te r alboflavum
Pro taminobac te r r u b r u m
Nocardia blackwelli
Nocardia blackwelli
CONSTANTS m . p . ° [ a ] D
—
—
-
-
-
-
-
—
-
-
-
-
231-234
-
-
231-233
—
-
—
-
-
-
235-239
—
—
-
-
-
-
-
-
-
-
-
-
-
+170[d]
-
-
—
-
-
-
-
-
-
-
—
R E F .
L-525
S-864; S-867
C-100; C-101
S-873
K-477
H-399
S-857
S-863
S-863
W-1072; K-456
S-901
C-125
V-1055; W-1102
S-948
H-324
W-1101; O-700; H-388
W-1101
W-1096
W-1096
S-943
S-866
S-866
S-943
S-943
129
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
^ 21 " 26^5
1 ^21 "26^6
NAME OF REACTION PRODUCT
prednisone
prednisone - 4-C 1
17a,21-dihydroxy-l , 5-pregna-d i e n e - 3 , l l , 2 0 - t r i o n e
11«, 17a, 21 - tr ihydroxy -1 ,4 ,6 -p regna t r i ene -3 ,20-d ione
l l /3 ,17a ,21- t r ihydroxy- l ,4 ,6 -pr egnatr iene -3 ,20 -dione
1 la, 20a, 21 - t r ihydroxy 9 /3 , l l / 3 -ox ido- l ,4 ,6 -p regna-t r i en -3 -one
17a, 20/3,21 - t r ihydroxy-9/3, l l /3-oxido-l ,4 ,6-pregna-t r i en -3 -one
16α, 17α, 21 - t r ihydroxy-1,4,9(11)- p r egna t r i ene -3,20-dione
11/3,14a-dihydroxy-3,20-diketo-4-pregnen-18-oic acid (18—*11) lactone
11/3,21-dihydroxy-3,20-diketo -4 -pr egnen -18 -oic acid (18—»11) lactone
11/3,14a, 21 - t r i hyd roxy-3 ,20 -d ike to - l ,4 -p regnad ien-18-al
6/3,17a, 21 - t r ihydroxy-1 ,4 -p regnad i ene -3 , l l , 20 - t r i one
7α, 17α, 21- t r ihydroxy-1 ,4-pregnadiene -3,11,20-tr ione
14a, 17a, 21- t r ihydroxy-1 ,4 -p regnad iene -3 , l l , 20 - t r i one
15/3 ,17a,21- t r ihydroxy- l ,4-pregnadiene-3 ,11,20- t r ione
9a, 11/3,17a, 21 - te t rahydroxy -1 ,4 ,6-pr egnatr i e n e - 3 , 2 0 -dione
11/3,14α, 17α, 21 - te t rahydroxy-1,4,6-pr egnatr i e n e - 3 , 2 0 -dione
J
TRANSFORMATION
3 a - O H - 3 - C = 0 ; Δ^4(5/3-Η); 21 -OAc-21-OH
Δ1
21-OAc^21-OH
2 1 - 0 - i - B u - 2 1 - O H
11a-OH
Δ1
2 0 - C = O - 2 0 a - O H
20-C=O-20/3-OH
3/3-OAc—3-C=0; 21 -OAc-21 -OH; AS 4 (5a -H)
14a-OH
d, l -»d-21-OH + l
14a-OH
6/3-OH
Δ1; 21-OAc - 21-OH
Δ1
Δ1
9a-OH
14a-OH
YIELD
% j -
54
-
—
—
-
—
—
—
—
—
-
—
-
—
—
ORGANISM
Nocardia blackwelli
Coryne bacter ium s implex
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Fusa r ium equiset t i
Bacil lus sphaer icus
Rhodotorulla r u b r a
Corynebac ter ium s implex
Bac te r ium havaniensis
P l eospora gaeumanni
Ophiobolus herpo t r ichus
Wojnowicia g ramin is
P leospora gaeumanni
Chaetomium funicolum
Baci l lus sphaer icus
Mycobacter ium smegmat i s
Bacil lus sphaer icus
Helicostylum p i r i fo rme
Helicostylum p i r i fo rme
CONSTANTS m.p.° [ α ] ρ |
- -
— -
- -
_ _
- -
239-243 +100fd]
_ —
— —
+9[c]
— —
205-222 +117[a]
— —
- -
- -
- ~
- -
— —
R E F .
S-939
C-120
N-690
N-690
M-557
G-310
G-303
G-303
O-705
W-1108
W-1101;
W-1102
W-1102 W-1108
C-108
N-687
S-874; S-873
C-126 1
G-302
G-302
130
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C21H2606
C21H2G06C1F
C21H2606F2
C21H27Ö3Br
C21H2703C1
C21H2703F
C21H2703N
C21H2704Br
C21H2704C1
i NAME OF REACTION
PRODUCT
l l /3 ,16a ,21- t r ihydroxy-3 ,20-diketo-4-pregnen-18-oic acid (18 —11) lactone
12a-chloro-6a-f luoro-16a, 17a, 21 - tr ihydroxy-4-pregnene-3,11,20-trione
6α, 12α-difluoro-11/3,16a, 17a, 21 - tetr ahydr oxy -1,4 -pr egna -diene-3 ,20-dione
9a-bromo-11/3-hydroxy-1,4-pregnadiene-3 ,20-dione
9a-chloro-l>/3-hydroxy-l ,4-pregnadiéne-3 ,20-dione
6a -fluor o -lia -hydroxy -1,4 -pr egnadiene -3 ,20-dione
6a -fluor o-H/3- hydroxy -1 ,4-pregnadiene -3 ,20-dione
6a-f luoro-17a-hydroxy-1,4-pr egnadiene -3 ,20-dione
6/3-f luoro-l la-hydroxy-l ,4-pr egnadiene -3 ,20-dione
6/3-fluoro-ll/3-hydroxy-l,4-pr egnadiene-3,20-dione
9a-fluor 0-11/3-hydroxy-1,4-pr egnadiene-3,20-dione
9a -fluoro -14a -hydroxy - 4 -pregnene -3,11,20-tr ione
17/3,20a -oxido-16 -oximino -1,4 -pregnadien-3 -one
12a -aza -C-homo- l , 4 -p regna -d iene-3 ,12 ,20- t r ione
9a -bromo -11/3,21 -dihydroxy -1,4 -pr egnadiene - 3 , 2 0 -dione
12a-bromo-16a-hydroxy-4-pregnene -3,11,20-tr ione
9a-chloro-11/3,17a-dihydroxy -1,4 -pregnadiene -3 ,20-dione
9a -chloro -11/3,21-dihydroxy -1,4 -pregnadiene -3 ,20 -dione
12a -chloro -16a -hydroxy -4 -pregnene-3 ,11,20- t r ione
TRANSFORMATION
16a -OH
21-OH
16a-OH
Δ1
Δ1
Δ1
Δ1
Δ1
Δ1
Δ1
1
Δ
Δ1
14a-OH
Δ1
3 / 3 - O H - 3 - C = 0 ; Δ 1 , 4 (5a-H)
21-OAC-21-OH
16a-OH
Δ1
Δ1
Δ1
16a-OH
YIELD %
-
—
—
-
-
—
-
-
-
-
-
_
—
62
—
-
—
—
ORGANISM
Pes ta lo t ia funer a
Ophiobolus herpot r ichus
Streptomyces roseochromogenus
Nocardia aurant ia
Corynebacter ium simplex
Corynebacter ium hoagii
Septomyxa affinis
Septomyxa affinis
Septomyxa affinis
Septomyxa affinis
Septomyxa affinis
Corynebacter ium simplex
P leospora gaeumanni
Bacil lus sphaer icus
Nocardia sp.
Corynebacter ium hoagii
St reptomyces roseochromogenus
Corynebacter ium hoagii
Corynebacter ium hoagii Nocardia coral l ina
Streptomyces roseochromogenus
CONSTANTS m . p . ° [or]D
_ __
- -
- -
- -
- -
- -
- -
- -
- -
- -
- -
- -
183-185 +48[m]
— —
- -
— —
— —
R E F .
W-1091
W-1091
F-261
F-261
H-379
H-379
C-91
C-91
B-34
C-91
C-91
H-379
W-1108a
N-686
M-563
N-668
F-256
H-379
N-668
H-399
F-257
131
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C 2 1 H 2 7 0 4 F
C21H2704FS
C21H2704N
1 C21H27OsBr
C21H2705C1
C 2 1 H 2 7 0 5 F
NAME OF REACTION PRODUCT
9a- f luoro- l l /3 ,17a-d ihydroxy-1,4 -pregnadiene -3 ,20 -dione
9a - f l uo ro - l l ß , 21 -d ihyd roxy -1 ,4-pregnadiene-3 ,20-dione
12a-f luoro- l l /3 ,21-dihydroxy-1,4 -pregnadiene -3 ,20 -dione
6a- f luoro-15a-hydroxy-4-p regnene -3 ,11 ,20 - t r i one
6a- f luoro-16a-hydroxy-4-p regnene -3 ,11 ,20 - t r i one
9a-fluor o-21-hydroxy-4-p regnene -3 ,11 ,20 - t r i one
9a -fluoro-11/3,17a-dihydroxy-21 - m e r c a p t o - 1 , 4 - p r e g n a -diene-3 ,20-dione
12a-aza -17a-hydroxy-C-homo -1 ,4 -pregnadiene -3 ,12 ,20 - t r i one
6 /3 -bromo- l l /3 ,17a ,21- t r i -hydroxy-1 ,4-pregnadiene -3,20-dione
9 a - b r o m o - l l ß , 1 7 a , 2 1 - t r i -hydroxy-1 ,4-pregnadiene -3,20-dione
6a -chloro-11/3,17a, 21 - t r i -hydroxy-1 ,4-pregnadiene -3,20-dione
9 a - c h l o r o - l l / 3 , 1 7 a , 2 1 - t r i -hydroxy-1 ,4-pregnadiene -3,20-dione
2 - f luo ro - l l j 3 ,17a ,21 - t r i -hydroxy-1 ,4-pregnadiene -3,20-dione
6a - f l uo ro - l l j 3 , 17a ,21 - t r i -hydroxy-1 ,4-pregnadiene -3,20-dione
9a-fluoro-11/3,16a, 1 7 a - t r i -hydroxy-1 ,4 -p regnad iene -3,20-dione
9 a - f l u o r o - l l j 3 , 1 7 a , 2 1 - t r i -hydroxy-1 ,4 -p regnad iene-3,20-dione
TRANSFORMATION
Δ1
Δ1;
Δ ; 21 -OAc-21 -OH
15a-OH
16a-OH
21-OH
2 1 - S A C - 2 1 - S H
3i3-OAc-3-C = 0 ; Δ^Μδα-Η)
11/3,17a,21-triOAc - l l / 3 , 1 7 a , 2 1 - t r i O H
1
Δ
11/3-OH
1
Δ
AX(2a-F)
1 Δ ;
21-OAC-21-OH
1
Δ
1
Δ
YIELD %
-
-
—
-
-
-
—
17
—
—
—
—
—
53
-
64
-
-
""*"
ORGANISM
Coryne bacter ium simplex
Nocardia coral l ina
Bacil lus sphaer icus
Pénic i l l ium ur t i cae
St reptomyces roseochromogenus
Cercospore l la herpotr ichoides
Flavobacter ium dehydrogenans
Nocardia sp.
F lavobacter ium dehydrogenans
Corynebacter ium simplex
Cunninghamella bainier i
Corynebacter ium s implex
Nocardia coral l ina
Septomyxa affinis
Septomyxa affinis
Septomyxa affinis
Bac te r ium havaniensis
Bac te r ium mycoides
Bacil lus lentus
Baci l lus sphae r i cus
Bac te r ium cyclo-oxydans
Bac te r ium havaniensis
CONSTANTS m . p . ° [ûf]D
-
-
—
-
-
-
~
260-262
—
—
195-196
—
-
202-204
202-204
208-213
275-279
265-269
-
—
-
-
—
-
-
-
—
+ 45|c]
_
—
+ 61fdl
—
-
+ 7 3td]
+ 92[d]
+ 92[d]
+ 51
+109[c|
-
~
REF.
H-379; N-668
H-399
T-985; W-1083
A-31
B-35
L-490
N-685
M-563
N-690
N-668 1
R-770
N-668
H-401
S-924
M-647
H-396
F-238
F-238
R-750
S-942; N-669
K-480
F-233
132
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C21H2705F
C21H2705N
C 2 1 H 2 7 0 6 0
C21H2 706F
NAME OF REACTION PRODUCT
9a - f l uo ro - l l / 3 , 17a ,21 - t r i -hydroxy-1 ,4-pr egnadiene -3,20-dione
12a-f luoro- l l /3 , 14α, 1 7 a - t r i -hydroxy-1 ,4-pregnadiene -3,20-dione
12a- f luoro - l l j3 ,17a ,21- t r i -hydroxy-1 ,4-pregnadiene -3,20-dione
1 6 ß - f l u o r o - l l ß , 1 7 a , 2 1 - t r i -hydroxy-1 ,4-pregnadiene -3,20-dione
9 a - f l u o r o - l l ß , 1 7 a , 2 1 - t r i -hydroxy-1 ,5-pregnadiene -3,20-dione
2a -f luor o -17a, 21 -dihy dr oxy -4 -pr egnene - 3 , 1 1 , 2 0 - t r ione
21-hydroxy-17/3,20a-oxido-16-oximino-4-pregnene-3,11 -dione
9 a - c h l o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 -te t r any dr oxy -1 ,4 -pr e gna -diene-3,20-dione
1 2 a - c h l o r o - 1 6 a , 1 7 a , 2 1 - t r i -hydroxy-4-pr egnene-3 ,11 ,20- t r ione
9a-f luoro- l l /3 ,16a , 1 7 a a - t r i -hydroxy-17aß-hydroxy-methyl -D-homo-1 ,4 - and ro -stadiene -3 ,17 -dione
TRANSFORMATION
Δ1
1
Δ ; 21-OAC-21-OH
20/3-OH^20-C=O
14a-OH
1
Δ
1
Δ
Hj3,17a ,21- t r iOAc -11 /3 ,17a , 21-tr iOH
Δ ' - Η
21-OAc->21-OH
1
Δ
16a-OH
1
Δ ; 1 6 a , 1 7 a , 2 1 - t r i - O H -20-C=O— 16a ,17aa-dihydroxy-17a/3-hydr oxy methyl -D -homo-17-C=Q
YIELD %
20
41
-
36
70
-
-
-
-
-
—
—
—
—
8
—
—
—
ORGANISM
Bacter ium mycoides
Corynebacter ium s implex
Corynebacter ium s implex
Didymella lycopers ic i
Nocardia coral l ina
Nocardia r e s t r i c t u s
Nocardia sp.
Bacter ium havaniensis
Bac te r ium mycoides
Didymella lycopers ic i
Mycobacter ium rhodocrous
P leospora gaeumanni
Bacil lus sphaer icus
Pro taminobac te r alboflavum
Fla vo bac ter ium dehydrogenans
Streptomyces sp„
Flavobacter ium dehydrogenans
Nocardia coral l ina
Streptomyces roseochromogenus
Bacter ium cyclooxydans
CONSTANTS m.p.° [α]Ό
265-269d
247-250
263-266
254-256
265-269
-
-
-
263-266
-
—
—
—
—
-
—
—
-
+ l l l [ e ]
—
+ 103[e]
+ 92[m]
+ l l l [ e ]
-
-
-
+108[d]
-
—
—
—
—
-
—
—
—
R E F .
F-240
H-389; N-671
N-668; N-665; N-669
W-1096
H-403; H-399
S-885
T-1005
F-233
F-240
V-1052
G-294
W-1103
H-380
B-51
N-690
H-402
N-686
H-399
F-256
G-297
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
133
EMPIRICAL FORMULA
NAME OF REACTION PRODUCT
9a- f luoro- l l /3 ,16a , 17aa - t r i -hydroxy -17a/3-hydroxy-methy 1-D-_homo - 1 , 4 - andr o-stadiene - 3 , 1 7 - dione
6 a - f l u o r o - l l a , 1 6 a , 1 7 a , 2 1 -t e t r ahyd roxy -1 ,4 -p r egna -die ne -3 ,20 -dione
6 a - f l u o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 -t e t r ahyd roxy-1 ,4 -p regna -d iene-3 ,20-dione
9 a - f l u o r o - 6 | , ll/3,17a,21-tetra-hydroxy - 1 , 4 - p r egnadiene-3,20-dione
9o-f luoro- l l ]3 ,14a , 1 7 a , 2 1 -t e t r ahyd roxy -1 ,4 -p regna -diene - 3 , 20 -dione
9 a - f l u o r o - l l ß , 1 5 j 3 , 1 7 a , 2 1 -t e t r ahydroxy-1 ,4 -pr egna-diene-3 ,20-dione
9a-f luoro- l l /3 ,15/3 ,16a ,21-t e t r ahyd roxy -1 ,4 -p r egna -diene -3 ,20-dione
9 a - f l u o r o - l l j 3 , 1 6 a , 1 7 a , 2 1 -t e t r a h y d r o x y - 1 , 4 - p r e g n a -diene-3 ,20-dione (triamcinolone)
TRANSFORMATION
1
Δ
11a -OH
11/3-OH
16a-OH
6 £ , l l j 3 , 1 7 a , 2 1 - t e t r a -O A c - > 6 | , l l / 3 , 1 7 a , 2 1 -tetraOH
14a-OH
1
Δ
1
Δ
1
Δ
16a-OH
20j3-OH^20-C=O
YIELD
% i ~~
-
-
—
48
5
—
43
10
-
65
—
-
30-70
-
20
-
ORGANISM
Nocardia cora l l ina
Rhizopus n igr icans
Cunninghamella bainier i
S t reptomyces roseochromogenus
Flavo bac ter ium dehydrogenans
Helicostylum p i r i fo rme
P leospora gaeumanni
Bacil lus sphaer icus
Bacil lus sphaer icus
Bac te r ium cyclo-oxydans
Bac te r ium havaniensis
Bac te r ium mycoides
Coryne bac te r ium s implex
Mycobacter ium rhodocrous
Nocardia coral l ina
Nocardia sp .
Nocardia i ta l ica
St reptomyces cal ifornicus
St reptomyces roseochromogenus
Bac te r ium cyclo-oxydans
CONSTANTS m.p.° [e]pl
254-255d
—
-
—
—
—
253-255
-
-
—
-
-
-
248-250
-
—
—
-
—
—
—
-
-
-
—
-
-
-
+ 71[a]
-
R E F .
S-910
R-771
R-771
H-399; M-531
G-309
N-669
W-1108a
N-669
N-669
G-296; G-297; L-505; R-779; S-908
F-233
F-240
B-61 ; S-908; G-296; H-399
T-1002; G-296
B-61 ; H-399; O-704
T-1005
S-918
L-491
T-1002
G-294; 1 G-296
C21H2705F
134
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C 2 1 H 2 7 0 6 F
^ 2 l " 2 8 ^ 2
NAME O F REACTION PRODUCT
tr iamcinolone
12a - f luo ro - l l j 3 ,16a ,17a ,21 -t e t r ahydroxy-1 ,4 -p regna -diene -3 ,20-dione
9a - f l uo ro -16a ,17a , 21 - t r i -hydroxy-4-pregnene-3 ,11 ,20- t r ione
17ß-hydroxy- 17α -methy l -16-methylene -1 ,4 -andr osta -dien-3-one
17/3-hydroxy-17a-vinyl-1,4-andr ostadien -3 -one
17a-ethinyl-17/3-hydroxy-4-andros ten-3-one
1,4 -pregnadiene -3 ,20 -dione
TRANSFORMATION
20/3-OH-20-C=O
20/3-OH-20-C = O; Δ1
16a-OH
16a-OH
1
Δ
1
Δ
3/3-OH-*3-C=0; Δ 5 - * Δ 4
1
Δ
YIELD %
-
-
-
-
—
-
~
51
-
70
-
-
-
-
-
-
-
-
60
-
17
ORGANISM
Corynebacter ium simplex
Mycobacter ium rhodocrous
Bac te r ium cyclo-oxydans
Corynebacter ium s implex
Streptomyces argenteolus
Streptomyces roseochromogenus
Streptomyces sp„
Coryne bacter ium simplex
Didymella lycopers ic i
Micrococcus dehydrogenans
Actinoplanes mis sour i ens i s
Bacil lus sphaer icus
Bac te r ium havaniensis
Bac te r ium mycoides
Calonectr ia decora
Corynebacter ium s implex
Cylindrocarpon radic icola
Fusa r ium solani
Gloeosporium ol ivarum Mycobacterium smegmat i s
Nocardia coral l ina
Nocardia r e s t r i c t u s
CONSTANTS m.p.° [α]Ό
-
-
-
-
—
-
-
145-148
165-166
264-266
144-147
-
-
-
151-152
-
-
151
149-151
150-153
-
150-151
-
-
-
-
—
-
—
-101[d|
-
-
-
-
-
-
+120[e]
~
-
+122[c]
+ 120[e|
-
—
R E F .
G-294; G-296
G-294; G-296
G-294; G-296
G-296
H-380
F-257
S-788
B-76
W-1109 1
C-84
M-536
S-942; H-399
F-233
F-240
V-1053; W-1096
H-399
P-733
N-663
K-465
S-820; S-873
H-399
S-885
135
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
C2iH2802
^ 2 l " 2 8 ^ 3
NAME O F REACTION PRODUCT
1 ,4-pregnadiene-3 ,20-dione
1,4 -pregnadiene -3 ,20 -dione -7ö-H3
1,4 -pregnadiene -3 ,20 -dione -I60-H3
1,4 -pregnadiene -3 ,20 -dione -l l a - H 3 , 12ö-H3
l l o - h y d r o x y - 1 , 4 - p r e g n a -diene -3 ,20-dione
11/3-hydroxy-l, 4 -p regna-diene -3 ,20 -dione
17o-hydroxy-1 ,4 -pregna-d iene-3 ,20-dione
21-hydroxy-1 ,4 -p regna-diene -3 ,20 -dione
TRANSFORMATION
Δ1
1,4 Δ (5α)
Δ1,4(5/3)
3 j 3 - O H ^ 3 - C = 0 ; Δ1
3 j3-OH-3-C = 0 ; Δ 5 - ^ Δ 4 ; Δ1
3 ß - O A c ^ 3 - C = 0 ; Δ 5 - Δ 4 ; Δ1
2 0 ß - O H ^ 2 0 - C = O ; 3j3-OH^3-C = 0 ; Δ 5 - > Δ 4 ; Δ1
Δ1
1
Δ
Δ1
1
Δ
Δ1
Δ1
Δ1
YIELD
% ι 20
—
-
-
45
49
50
1
41
-
-
-
-
-
-
8(cr.)
73
-
49
66(cr.)
-
—
ORGANISM
Nocardia sp.
Septomyxa affinis
S t reptomyces lavendulae
Nocardia sp.
Nocardia sp.
Corynebacter ium s implex
Bacil lus pulvifaciens
Bacil lus pulvifaciens
Corynebacter ium s implex
Baci l lus sphaer icus
Bacillus sphaer icus
Bacillus sphaer icus
Bacter ium cyclo-oxydans
Bac te r ium havaniensis
Bacter ium mycoides
Corynebacter ium s implex
Septomyxa affinis
Bacil lus sphaer icus
Septomyxa affinis
Septomyxa affinis
Actinoplanes mi s sou r i ens i s
Baci l lus sp.
Bacil lus sphaer icus
Bac te r ium havaniensis
CONSTANTS m.p.° [<*]D
150-151
—
-
-
150-152
150-152
150-155
-
152-153
-
-
-
228-230
-
-
228-230
232.5-234
232-234
-
179-180
183-187
-
-
-
—
-
-
-
-
+112[e]
-
+122[cl
-
-
-
+ 93[c]
-
-
+ 93[c]
+117[cl
—
-
-
+108[a]
-
-
R E F .
S-897; S-888
W-1072; H-399; V-1048
P-733
S-888
S-888
N-665
T-1027; 1-420
T-1027; 1-420
N-665; C-128
G-323
G-323
G-323
K-480
F-233
F-240
T-995
E - 2 0 8 ; W-1072; K-456
S-942
W-1072
W-1072
M-536
S-848
S-942
F-233
136
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
1
EMPIRICAL FORMULA
C21H2803
NAME OF REACTION PRODUCT
21 -hydroxy-1,4-pregnadiene -3,20-dione
21-hydroxy- l , 4 -p regnad iene -3,20-dione
1 l a -hyd roxy -4 ,6 -p regna -diene-3,20-dione
15a -hydroxy-4 ,9 ( l l ) -p regna -diene-3 ,20-dione
16a - hydr oxy -17/3 - methyl -18 -nor-4 ,13-17a-pregnadiene -3,20-dione
16/3-hydroxy-17ß-methyl-18-nor -4 ,13-17a-pregnadiene-3,20-dione
21-hydroxy-4 ,14-pregna-diene-3,20-dione
21-hydroxy-4 ,16-pregna-diene-3 ,20-dione
3 -hydroxy-9 ,10-seco-1,3, 5(10) -p regna t r i ene-3,20-dione
TRANSFORMATION
Δ1
1
Δ ; 21-OAC-21-OH
Δ 1 ' 4 (5ß-H)
21-OH
11a-OH
15a-OH
3 ß - O H - 3 - C = 0 ; Δ 5 -*Δ 4
3 ß - O H - 3 - C = 0 ; Δ 5 - Δ 4
21-OH
21-OH
1
Δ ; 9a-OH; rev . aldol.; enol.
YIELD %
ca. 100
-
88
60(cr.)
-
-
26
-
—
-
-
-
68(cr0)
22-51
-
7
27
-
—
—
<1
ORGANISM
Calonectr ia decora
Calonectr ia decora
Corynebacter ium simplex
Didymella lycopers ic i
Gliocladium ro seum
Helminthosporium turc icum
Ophiobolus he te ros t ropus
Pseudomonas dacunhae
Septomyxa affinis
My co bacter ium smegmat i s
Mi cromonospor a chalcea
Pro taminobac te r alboflavum
Pro taminobac te r r u b r u m
Ophiobolus herpot r ichus
Rhizopus n igr icans
Gibberel la saubinett i
F lavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Ophiobolus herpotr ichus
Cercospore l la herpotr ichoides
Kabatiella phoradendr i
Mycobacterium smegmat i s
CONSTANTS m.p.° [α]Ώ
189-195d
185-192
-
185-195
185-191
-
-
184-189
-
-
-
-
-
185-192
160-162
-
138-140
128-129
182-184
—
-
+120[c]
-
-
+110[m]
-
-
+110[al
-
-
-
-
-
+120[c]
+ l l l [ c l
-
+187[d] + 82[c]
+ 141[d] +136[c]
-
—
—
R E F .
V-1053
W-1096
N-665
W-1096
S-857
S-857
S-857
S-848
W-1072
S-873
S-867
S-866
S-866
W-1101
P-730; M-601
M-599
S-839
S-839
M-576
L-490
L-498
S-820
137
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
^21 " 2 8 ^ 3
C 2 1 H 2 8 0 3 BrF
C2 1 H2 8 0 4
NAME O F REACTION PRODUCT
l l /3 ,21 -d ihydroxy- l ,4 ,17 (20) -p regna t r i en -3 -one
11/3,12/3-oxido-4-pregnene-3,20-dione
17a -b romo-6a - f luo ro - l l / 3 -hydroxy-4 -p regnene -3 ,20 -dione
17/3-hydroxy-4-androstene-3,11 -dione aceta te
6/3,1 la -dihydroxy -1 ,4 -pr egnadiene-3 ,20-dione
11/3,21-dihydroxy-1,4-pr egnadiene -3 ,20 -dione
16α ,21-d ihydroxy-1 ,4-pr egnadiene -3 ,20 -dione
17a, 21-d ihydroxy-1 ,4 -pr egnadiene-3,20-dione
TRANSFORMATION
Δ1
Δ 1 Χ - 1 1 ^ , 1 2 ^ -oxide
llj3-OH
17/3-Ac^l7/3-OAc
6/3-OH
1
Δ
Δ1
1
Δ
YIELD %
80(cr.)
1
—
12
-
—
-
42
-
33(cr.)
44
-
-
-
-
3
-
—
—
33
-
~
42
ORGANISM
Septomyxa affinis
Curvular ia lunata
Curvular ia lunata
Cladosporium r e s inae
Chaetomium funicolum
Chaetomium succineum
Bacil lus pulvifaciens
Bacil lus sp.
Bacil lus sphaer icus
Calonectr ia decora
Corynebacter ium simplex
Gliocladium r o s e u m
Helminthospor ium tu rc icum
Mycobacter ium phlei
Nocardia cora l l ina
Ophiobolus he te ros t ropus
Pseudomonas dacunhae
Bac te r ium havaniensis
Bacter ium mycoides
Corynebacter ium s implex
Azotomonas f luorescens
Bacillus lentus
Bacillus pulvifaciens
Bacil lus pulvifaciens
CONSTANTS m . p . ° [ a ] D
149-153
-
—
167.5-169
-
—
-
210-218
-
216-220
227.5-230.5
208-218
-
217-218
-
-
207-211
-
-
—
-
240-242
-
217.5-219
-
—
-
-
—
-
+150[el
-
+158[e]
+173 [m]
+140[e]
-
+154[el
-
-
+136[e]
-
-
-
-
+80[dl
-
+70[cl
R E F .
W-1072; M-647; K-456; R-766
K-484
R-759
F-250
C-108
C-108
1-420
S-848
S-942
V-1053; W-1096 H-389; N - 6 7 1 ; N-665 S-857
S-857
S-873
H-399
S-857
S-848
F-233
F-240
H-376
T-989
R-750
1-420
T-1027 i
138
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
^2 l "28^4
NAME OF REACTION PRODUCT
17ö ,21 -d ihydroxy- l , 4 -pregnadiene -3 ,20-dione
TRANSFORMATION
Δ1
YIELD %
56
43
-
-
-
-
-
53
—
32
65
-
-
-
-
60(cr.)
-
-
-
—
—
-
-
24
—
ORGANISM
Bacil lus sp. Bacil lus sphaer icus
Bacil lus sphaer icus
Bacillus subti l is
Bacter ium cyclooxydans
Bacter ium havaniensis
Bacter ium mycoides
Calonectr ia decora
Corynebacter ium simplex
Corynebacter ium simplex
Cylindrocarpon radic icola
Flavobacter ium sp.
Fusa r ium javanicum
Fusa r ium solani
Fusa r ium solani
Fusa r ium solani
Gliocladium r o s e u m
Gloeosporium ol ivarum
Graphiola cyl indrica
Helminthosporium gramineum
Helminthosporium sp.
Helminthospor ium zizaniae
Hypomyces solani
Mycobacterium f la vu m
Mycococcus sp.
Nocardia coral l ina
CONSTANTS m.p.° [a]D
234-238
226-230
-
-
-
-
227-233d
246-250d
—
240-242
-
242-244
229-233
-
226-230
232-236
225-230
-
—
—
224-229
-
—
-
—
+75|c |
+77[e|
—
-
—
-
+76[e|
+76[c|
—
+57[c|
-
—
+76[e]
-
+77[e]
+80[cl
+77lel
-
—
—
+ 77[e |
-
—
-
—
REF.
S-848 S-942; i H-399 K-444
L-522
K-480
F-233
F-240
W-1096; V-1053
H-389; N - 6 7 1 ; N-665
H-399; L-522
F-275
1-430
F-275
V-1053
V-1048; S-835
K-462
S-857
K-464; K-465
K-465
K-460
S-857
K-460
L-525
C-100
1-429
H-399
139
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
("21 " 2 8 * Λ
NAME O F REACTION PRODUCT
1 la, 21 - dihy dr oxy -1 ,4 -pregnadiene-3 ,20-d ione
6/3,12a-dihy dr oxy -4 ,9 (11 ) -pr e gnadiene - 3 , 2 0 - dione
TRANSFORMATION
^
A 1 ; 2 1 - O A c - 2 1 - O H
Δ 1 ' 4 (5αΗ)
Δ1,4(5/3Η)
3 J 3 - O A C — 3 - C = O;
2 1 - O A C - 2 1 - O H
6j3-OH; 12a-OH
YIELD %
-
—
—
12
-
—
-
-
20
70-80
-
-
-
—
-
-
-
-
-
-
10-15
25
51(cr.)
—
ORGANISM
Ophiobolus he te ros t ropus
Pseudomonas boreopolis
Pseudomonas chlor or aphis
Pseudomonas dacunhae
Pseudomonas oleovorans
Pseudomonas sp.
Rhizoctonia solani
Septomyxa affinis
Septomyxa affinis
Septomyxa affinis
Se r r a t i a m a r c e s c e n s
S te reum fasciatum
St reptomyces flaveolus
S t rep tomyces lavendulae
St reptomyces sp .
Volutella ci l iata
Cylindrocarpon rad ic ico la
Mycobacter ium smegmat i s
Nocardia blackwellii
Nocardia blackwellii
Corynebac te r ium s implex
Corynebac ter ium s implex
Aspergi l lus nidulans
Col le totr ichum phomoides
Thamnidium elegans
CONSTANTS m . p . ° [ a ] p |
-
—
—
220-231
-
—
221
-
238-242
-
~
233-234
235-239d
-
-
-
-
235-236
-
-
238-240
246-249
231-232
—
-
-
—
+8205[mj
-
—
+72[cl
-
+70[cl
-
-
+80[cl
+75[el
-
-
-
-
+72[al
-
-
-
+76[c]
+107[c]
—·
R E F .
S-857
T-960
N-648
S-848
T-960
N-652; U-1039; 1-414
T-956
S-835; V-1048
W-1072
S-901
T-960
T-959
K-470
S-835; V-1048
K-470
L-525
F-275
S-873
S-943
S-943
C-128; C-115
N-665
F-277
F-277
F-277
140
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
^ 2 1 " 2 8 ^ 4
NAME OF REACTION PRODUCT
6 /3 ,X-d ihydroxy-4 ,9 ( l l ) -pr egnadiene -3 ,20 -dione
17a,21 -dihydroxy-4,9(11) -pr egnadiene -3 ,20 -dione -l l , 1 2 a - H 3
6/3,21 -dihydroxy-4,17 (20)-pregnadiene-3 ,11 -dione
9a ,21-dihydroxy-4 ,17(20)-pr egnadiene-3,11-dione
21-hydroxy-ll /3,12/3-oxido-4-pregnene-3 ,20-d ione
7/3-hydroxy-16a, 17a-oxido -4-pregnene-3 ,20-d ione
1 la-hydroxy-16a ,17a-oxido -4-pregnene-3 ,20-d ione
9a-hydroxy-4-pregnene-3 ,11 ,20- t r ione
15a-hydroxy-4-pregnene-3 ,11 ,20- t r ione
17a-hydroxy-4-pregnene-3 , 1 1 , 2 0 - t r ione
21-hydroxy-4-pregnene-3 ,11 ,20- t r ione
15a-hydroxy-4-pregnene-3 ,12 ,20- t r ione
TRANSFORMATION
6/3-OH; X-OH
2 1 - O A c - 2 1 - OH
6/3-OH ; 11/3-OH - 11-C=0
9a-OH; 1 1 / 3 - O H - 1 1 - C = 0
21-OH
7/3-OH
11a-OH
9a-OH
15a-OH
17a-OH
21-OH
15a-OH; 12a-OH - 1 2 - C = 0
YIELD %
-
—
14-29
-
59
—
32
19
—
9
31-73
78
-
-
-
—
-
-
38
-
51(cr.)
ORGANISM
Colletotr ichum p ho mo ides
Cur uvular ia lunata
Rhizopus a r r h i z u s
Cunninghamella blakesleeana
Helicostylum p i r i fo rme
Cercospore l l a herpotr ichoides
Wojnowicia g ramin is
Pénic i l l ium sp„
Botryodiplodia theobromae
Didymocladium te rna tum
Rhizopus n igr icans
Rhizopus n igr icans
Rhizopus n igr icans
Rhizopus ref lexus
Ascochyta linicola
Calonectr ia decora
F u s a r i u m concolor
Pénic i l l ium ur t icae
Aspergi l lus sp.
Cephalothecium r o s e u m
Aspergi l lus niger
Aspergi l lus niger
Ophiobolus herpot r ichus
Calonectr ia decora
CONSTANTS m . p . ° [<*]D
250-252
—
252-254
-
219.5-221
—
164-166
229-232
—
246-247
247-249
235-237
238-238.5
-
—
224-228
227-229
-
178-179
-
170-176
235-239
+23[c]
—
+107[dl
-
+173[dl
—
+179[c]
+158.5[cl
—
—
+136[c]
+146[c]
+137[c]
-
-
+289[c]
+257[el
-
-
-
—
+261[c]
R E F .
F-277
K-484
H-344; H-341
H-344; H-342
H-344; H-342
L-490
D-157
T-1036
P-746
P-746
P - 7 2 7 ; M-644
E-223
B-52 ; D-161
M-644 |
S-828
S-810
M-599
B - 4 4 ; A-31 T-1010
M-600
Z-1124; Z-1123
R-783
M-584; W-1101
S-810
141
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C21H2804
C21H2804C12
C 2 1 H 2 8 ° 4 F 2
C 2 1 H 2 8 0 4 S
C 21 H 28 0 5
NAME O F REACTION PRODUCT
6/3 -hydr oxy -4 -pr egnene -3 ,15 ,20 - t r i one
7£,20/3-dihydroxy-3-keto-4-pregnen-18-o ic acid (18-^20) lactone
l l a ,20 /3 -d ihydroxy-3-ke to -4-pregnen-18-o ic acid (18->20) lactone
9 a , l l / 3 - d i c h l o r o - 1 7 a , 2 1 -d ihydroxy-5-pregnene-3,20-dione
9a , l l / 3 -d i f l uo ro -17a ,21 -d ihydroxy-5-pregnene-3,20-dione
l l /3 ,17a-d ihydroxy-21-m e r c a p t o - 1 , 4 - p r egnadiene -3 ,20-dione
1 7 a , 2 0 a , 2 1 - t r i h y d r o x y - l , 4 -pr egnadiene-3 ,11-dione
17a, 20/3,21 - t r i h y d r o x y - 1 , 4 -pr egnadiene - 3 , 1 1 -dione
6 /3 ,17a ,21 - t r i hydroxy- l , 4 -pr egnadiene -3 ,20 -dione
la, 1 la, 21 - t r ihydr oxy - 1 , 4 -pregnadiene-3 ,20-d ione
TRANSFORMATION
6/3-OH; 1 5 - C = 0 ; (via 15/3-OH)
7ξ-ΟΗ
11α-OH
21-OAc^21-OH
21-OAc^21-OH
2 1 - S A c - 21-SH
2 0 - C = O - 2 0 a - O H
20-C=O^20/3-OH
1 Δ
1
20-C=O^20/3-OH
Δ1
6/3-OH
7a-OH
YIELD %
0.5
—
—
—
—
22
—
-
69
75
60
-
-
-
-
-
-
-
ORGANISM
Pénic i l l ium sp.
Rhizopus n igr icans
Rhizopus n igr icans
Flavobacter ium dehydrogenans
F lavobacter ium dehydrogenans
F lavobac ter ium dehydrogenans
Rhodotorula longiss ima
Calonectr ia decora
F u s a r i u m sp.
Mycobacter ium flavum
Streptomyces albus
St reptomyces g r i seus
St reptomyces hydrogenans
Calonect r ia decora
F u s a r i u m sp.
Calonect r ia decora
Corynebac ter ium s implex
F u s a r i u m sp.
Gloeosporium ol ivarum
Mycobacter ium flavum
Baci l lus lentus
Chaetomium funicolum
Diplodia na ta lens is
CONSTANTS m.p.° [α]Ό
280-286
—
—
—
—
238-240d
—
-
184-185
184-185
—
-
-
177-180
-
-
-
229-231
+122[e]
—
—
—
—
+117[d]
;
-
+117[d]
+118[d]
—
-
-
-
-
-
-
-
R E F .
T-1036
L-488; L-489
L-488; L-489
N-691
N-691
N-685
C-110
S-951
S-951
C-100
K-459
C-110
L-522
S-951
S-951
S-951
H-389
S-951
K-465
C-100
R-750
C-108
T-997
142
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C 2 1 H2 8 0 5
NAME OF REACTION PRODUCT
l l ö , 17α, 21 - t r i hyd roxy -1 ,4 -pr egnadiene -3 ,20 -dione
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - l , 4 -pr egnadiene -3 ,20 -dione (prednisolone)
TRANSFORMATION
Δ1
11a-OH
11a-OH; 21-OAc^21-OH
1
Δ
YIELD %
25-50
~
-
61(cr.)
-
—
12
-
42
70
-
46
-
62
—
-
—
—
-
-
—
80
94(cr.)
90
—
ORGANISM
Corynebacter ium s implex
Aspergi l lus ochraceus
Beauveria sp.
Fusa r ium equiset i
Glomere 11a cingulata
Glo mere 11a lagenar ium
unidentified fungus
Glomerel la cingulata
Glomere l la lagenar ium
Azotobacter agi l is
Azotobacter indicus
Azotomonas f luorescens
Bacil lus lentus
Bacil lus pulvifaciens
Bacil lus pulvifaciens
Bacil lus sp.
Bacil lus sphaer icus
Bacil lus sphaer icus
Bac te r ium cyc lo-oxydans
Bac te r ium havaniensis
Bacter ium mycoides
Calonectr ia decora
Corynebacter ium hoagii
Corynebacter ium s implex
Corynebacter ium s implex
Corynebacter ium s implex
Corynebacter ium s implex
CONSTANTS m . p . ° [α]Ό
246-247d
-
-
206-208
-
-
222-223
-
—
-
235-237
220-222
~
228-231
—
233-236d
—
-
-
238-241
-
239-241d
240-241d
235d
-
+ 73 [m]
-
-
+ 76[d]
-
-
+ 76[m]
-
—
-
+100[d]
+ 99[d]
-
+ 98[m]
-
+100[d]
—
—
-
-
—
+107[dl
+102[d]
+100[d]
—
R E F .
H-389; H-384; N-665
V-1048; S-835
1-421
M-557
C-109
C-109
T-990
C-109
C-109
T-989
T-989
T-989
R-750
T-1027
1-420
S-848
S-942; H-399
K-468
K-480
F-233
F-240
W-1096
N-665
N-665
H-389; N-671
K-467
H-399
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C21H2805
NAME OF REACTION PRODUCT
Prednisolone
TRANSFORMATION
Δ1
α , Ι - α - Δ ^ 1
Ij4
Δ (5α-Η)
Δ1,4(5β-Ή)
YIELD %
-
84
75
-
-
46-68
-
-
77-80
55-62
—
-
-
-
-
—
-
-
-
-
-
-
-
-
ORGANISM
Didymella lycopers ic i
Didymella lycopers ic i
Flavobacter ium sp„
Gloeosporium ol ivarum
Graphiola cyl indrica
Micrococcus sp .
Micromonospora chalcea
Mycobacter ium smegmat i s
Mycobacter ium sp.
Mycococcus sp0
Nocardia cora l l ina
Nocardia sp.
P ro taminobac te r alboflavum
Pro taminobac te r r u b r u m
Pseudomonas chlororaphis
Septomyxa affinis
Se r r a t i a plymuthica
Streptomyces flaveolus
St reptomyces lavendulae
St reptomyces sp.
Didymella lycopers ic i
Calonectr ia decora
Nocardia blackwellii
P ro taminobac te r alboflavum
Pro taminobac te r rub rum
CONSTANTS m . p . ° [α]Ό
234-236 + 98[d]
238-241 —
- ~
~ -
236 +100[d]
- -
- -
196-198 +108[e|
- -
- -
- -
- -
- -
- -
- -
— —
- -
232-236d +100[d]
235-237 —
- -
234-236 + 98[d]
— -
- -
- -
R E F .
V-1052
W-1096
1-430
K-465
K-465
1-431
S-864; S-867
S-873
K-476
1-429
H-399
S-939
S-863
S-863
N-648
W-1072; M-647; K-456
T-960
K-470
F-272
K-470
W-1102
W-1096
S-943
S-866
S-866
143
144
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
CMH„805
NAME OF REACTION PRODUCT
Prednisolone
12 /3 ,17a ,21- t r ihydroxy- l ,4 -pr egnadiene -3 ,20 -dione
14a, 1 7 a , 2 1 - t r i h y d r o x y - l , 4 -pr egnadiene - 3 , 20 -dione
15 /3 ,17a ,21- t r ihydroxy- l ,4 -pregnadiene-3 ,20-dione
16a, 1 7 a , 2 1 - t r i h y d r o x y - l , 4 -pr egnadiene -3 ,20 -dione
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - l , 5 -pregnadiene-3 ,20-dione
17a ,20/3 ,21- t r ihydroxy-4 ,6-pregnadiene -3 ,11 -dione
14a, 1 la, 21 - t r ihydr oxy -4,9( 11)-pr egnadiene - 3 , 2 0 -dione
17a, 21-dihydroxy-l/3,11/3-oxido -5 ,9 -cyclopr egnane -3,20-dione
l l /3 ,21-d ihydroxy-3 ,20-dike to-4-pregnen-18-a l (18-^11) hemiaceta l (aldosterone)
TRANSFORMATION
3a-OH >3-C = 0 ; Δ1,4(5/3-Η)
11/3-OH
21-OH
Δ 1 ; 11/3-OH
1
Δ
1
Δ
14α-OH 1
Δ
1
Δ
21-OAC-21-OH
11/3,17α, 21-tr iOAc — 11/3, 17α, 21- t r iOH
20-C=O-+20/3-OH
14α-OH
11/3,21-diOAc-11/3,21-diOHj Δ ' - Ι Ι ^ - Ο Η - Ι / Β , 11/3-oxide
11/3-OH
d,l->d-21-OH + 1
YIELD %
-
-
19
11
—
-
-
20-30
-
2
10
—
-
-
—
—
26
—
-
ORGANISM
Nocardia blackwellii
Coniothyrium hel leborine
Cort ic ium sasaki i
Unidentified fungus
Ophiobolus herpotr ichus
Cort ic ium sasaki i
Pseudomonas oleovorans
Pseudomonas sp.
Bacil lus lentus
Corynebacter ium simplex
Bacil lus lentus
Mycobacterium smegmat i s
Unidentified fungus
Bacil lus sphaer icus
Bacter ium havaniensis
Bacter ium mycoides
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Curvular ia lunata
Curvular ia lunata
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Cunninghamella blakesleeana
Ophiobolus herpot r ichus
CONSTANTS m.p.° [a]D
-
-
232-236d
230-231
—
227-231
-
-
232-234
232-234
229-230
217-218
234-234.5
-
-
-
—
-
208-209; 204-205 (polymorph)
191-194
208-213
200-206
165-168
162-168
-
-
-
-
—
-
-
-
-
+132[cl
+107[ml
-
-
-
-
—
+126 [d]
—
- 14
- 14
+142[a]
R E F .
S-943
T-1004
H-350
T-990
W-1101; H-388; O-700
H-327
T-960
T-961; U-1040
R-750
R-749
R-750
S-872; S-873
T-990
C-126; C-127
F-233
F-240
N-690
N-690
G-306
B-65
G-292
R-777
W-1100
w-1102; V-1055
145
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
^ 2 l " 2 8 ^ 5
NAME OF REACTION PRODUCT
17a ,21-dihydroxy-9a , 11a-ox ido-4 -p regnene -3 ,20 -dione
17a ,21-dihydroxy-9a , 11a-ox ido-4 -p regnene-3 ,20-dione-11/3,12a-H3
6/3,12a-dihydroxy-9j3, 11/3-ox ido-4 -p regnene -3 ,20 -dione
17a,21-dihydroxy-9/3, l l /3-ox ido-4 -p regnene-3 ,20-dione
17a,21-dihydroxy-9/3 , l l /3-ox ido-4 -p regnene -3 ,20 -d ione - l l a , 12a -H3
16a, 21-dihydroxy-l l /3,12/3-ox ido-4 -p regnene -3 ,20 -dione
17a,21-dihydroxy-14a, 15a-ox ido-4 -p regnene -3 ,20 -dione
2/3,21-dihydroxy-16a,17a-ox ido-4 -p regnene -3 ,20 -dione
1 l a , 21 -dihy dr oxy -16a, 17a -ox ido-4 -p regnene-3 ,20-dione
17a ,21 -d ihydroxy- l -5ß -pregnene - 3 , 1 1 , 2 0 - t r ione
6/3,21-dihydroxy-4-pregnene-3 , 1 1 , 2 0 - t r ione
14a, 21-dihy dr oxy-4-pr egnene - 3 , 1 1 , 2 0 - t r ione
TRANSFORMATION
A 9 ( l l ) - 9 a , l l a - o x i d e
9 ( i l )
Δ -*9a, 11a-oxide; 2 1 - O A c - 2 1 - O H
9(11) Δ - 9 / 3 , 1 Iß -oxide; 6/3-OH; 12a-OH
9(11) Δ '->9|3,ll/3-oxide
9 (n ) Δ — 9/3,1 Iß-oxide; 21-OAc-* 21-OH
16a-OH
14
Δ —14a, 15a- oxide
2/3-OH
11a-OH; 21-OAC-21-OH
Δ4-5/3-Η
6β-ΟΗ; l l / 3 - O H - l l - C = 0
14a-OH
14a-OH; l l ß - O H - l l - C = 0
1
YIELD %
20
46
41(cr0)
-
—
11
26
-
—
-
~
—
—
14(cr.)
16(cr.)
36(cr.)
40(cr.)
ORGANISM
Nocardia sp.
Curvular ia sp.
Colletotr ichum p ho mo ides
Cunninghamella blakesleeana
Curvular ia brachyspor ia
Curvular ia lunata
Curvular ia lunata
St reptomyces roseochromogenus
Cunninghamella blakesleeana
Curvular ia lunata
Helicostylum p i r i fo rme
Mucor gr iseocyanus
Mucor pa ras i t i cus
Phycomyces blakesleeanus
Gnomonia f ragar iae
Rhizopus n igr icans
St reptomyces sp.
Sclerot ium hydrophilum
Absidia r e g n i e r i
Absidia r e g n i e r i
CONSTANTS m . p . ° [ûi]D
213-215
223
202-204
210-211
—
208-211
212-214
230-232
-
—
-
-
—
218-220
-
195-200
208-214
210-215
+ 85fd]
—
+ 5 I C 1
+ 13[d]
—
—
+158[cl
+135[dl
-
—
-
-
—
+127[m]
~
+146.5 [m]
+ 69[m]
R E F .
S-886
K-484
F-277
B-66
S-865
B-66; S-865; B-65
K-484
D-157
B-66; S-865
B-66; S-865
B-66; S-865
B-66; S-865
B-66; S-865
S-865
L-496
A-8
G-314
S-856
S-841
S-841; S-851
146
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C21 H28°5
C 2 l H 2 8 U 5 r 2
NAME OF REACTION PRODUCT
15/3, 21 -d ihydroxy-4-pregnene-3 ,11 ,20- t r ione
17a, 21 -dihydroxy -4 -pregnene-3 ,11 ,20- t r ione (cortisone)
17a, 21 -dihydroxy -16a-methyl -18-nor -4-pregnene -3 ,11 ,20- t r ione
6a ,21-d i f luoro- l l j3 ,16a ,17a-t r ihydroxy-4-pregnene-3,20-dione
TRANSFORMATION
15/3-OH; l l / 3 - O H - l l - C = 0
Δ1—H
21-OAC-21-OH
l l j 3 - O H - l l - C = 0
l l ß - O H - > l l - C = 0 ; 21-OAc-»21-OH
17a-OH
17a-OH; l l j3-OH-»l l -C = 0
11)3 -OH; l l j 3 - O H - l l - C = 0
21-OH
16a-OH
YIELD %
28(cr.)
21(cr.)
1
-
59
—
3
-
-
~
—
-
-
13
-
~
-
-
—
ORGANISM
Botryt is c inerea
Sclerot ium hydrophilum
Bacil lus mega te r ium
Bacil lus mega te r ium
Cunninghamella blakesleeana
Cunninghamella e legans
Cunninghamella e legans
Cephalothecium r o s e u m
Trichothecium r o s e u m
Cephalothecium r o s e u m
Trichothecium r o s e u m
Absidia sp0
Botryt is c inerea
Cort ic ium sasaki i
Cunninghamella blakesleeana
Cunninghamella blakesleeana
Cunninghamella sp0
Curvular ia lunata
Rhizoctonia sp.
St reptomyces fradiae
Colletotr ichum linde muthianum
Streptomyces roseochromogenus
CONSTANTS m.p.° [α]Ό
189-195
195-200
215-220d
-
211-213
-
-
206-216
~
-
-
-
226-227
-
—
-
-
-
—
+180[m]
+190[m]
—
-
-
—
-
-
-
-
—
-
-
-
-
-
-
—
—
R E F .
S-842
S-856
H-382
S-948
H-344
E-225
E-225
M-600
M-584
M-600
M-584
C-98; H-334
C-98
H-327
M-601
M-556; 0 -696; H-339; M-555; M-641; S-919
C-98
C-98
G-312; G-313
H-328
A - l l
M-532
147
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C21 H28°6
NAME OF REACTION PRODUCT
11/3,16a, 17aa- t r ihydroxy-17a/3-hydroxymethyl-D-homo - 1 , 4 -andr ostadien - 3 , 17-dione
*6/3, 11/3,17α ,21- te t rahydroxy-1,4 -pr egnadiene -3 ,20-d ione
7a, 11/3,17a, 21- te t r ahydr oxy -1,4 -pr egnadiene -3 ,20-dione
11/3,14a, 17a, 21 - te t r ahydr oxy-1,4 -pr egnadiene -3 ,20-dione
1 l a , 15/3, 17a, 21 - te t r ahydr oxy-1,4 -pr egnadiene -3 ,20-dione
11/3,15/3,17a, 21-tetrahydroxy-1,4 -pr egnadiene -3 ,20-d ione
11/3,16a,17a,21 - te t r ahydr oxy-1,4 -pr egnadiene -3 ,20-dione
11/3,14a,21-tr ihydroxy-3 ,20-d ike to -4-pregnen-18-al (18 — 11) hemiaceta l
11/3,17a, 21 - tr ihydroxy - 3 , 2 0 -diketo -4 -pr egnen -18 -al (18 - 11) hemiace ta l
14a, 17a,21-tr ihydroxy-9/3, l l /3-oxido-4-pregnene-3 , 20-dione
11/3,17a, 21- t r ihydroxy-14a , 15a-ox ido-4-pregnene-3 , 20-dione
2/3 ,17a ,21- t r ihydroxy-4-p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e (tentative)
6/3,17a, 21 - tr ihydroxy -4 -p r egnene -3 ,11 ,20 - t r i one (tentative)
7α, 17α, 21- t r ihydroxy-4-p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
La t e r , unpublished work has £
TRANSFORMATION
16a-OH ; 17a-OH-17/3-(20-C = 0 - 2 1 - O H ) -17aa-OH-17a/3-CH 2 OH-17-C=0
6/3-OH
7α-OH
Δ1
Δ1
Δ1
Δ1
16α-OH
14α-OH
d , l - d-17a-OH + 1
14a-OH; ΔΚ11) - , 9β, 11/3-oxide
11/3-OH; Δχ4-> 14a, 15a-oxide
11-C = 0 (via 11/3-OH); 2/3-OH
6/3-OH; 11-C = 0 (via 11/3-OH)
7a-OH
ihown this product to b
YIELD %
—
-
—
—
—
-
-
28
10
-
-
—
—
—
—
—
—
e 6/3,17
ORGANISM
Streptomyces roseochromogenus
Chaetomium cochliodes
Diplodia nata lens is
My co bacter ium smegmat i s
Bacil lus sphaer icus
Bacil lus sphaer icus
Bac te r ium havaniensis Bac te r ium mycoides
Corynebacter ium s implex
Nocardia coral l ina
St reptomyces cal ifornicus
St reptomyces roseochromogenus
P leospora gaeumanni
Tr ichothecium r o s e u m
Curvular ia lunata
Cunninghamella blakesleeana
Curvular ia lunata
Rhizoctonia solani
Rhizoctonia solani
Diplodia na ta lens is
a , 2 1 - t r i h y d r o x y - l , 4 - (
CONSTANTS m . p . ° [o?]D
—
—
227-229
—
—
-
-231-232
229-231
-
-
—
—
—
181-200
210-215d
—
regnadiene
—
-
+103.5['d|
—
—
-
-
+77 [m|
—
-
-
—
—
—
:
—
+113|d|
-
-3 ,11 ,20 -
REF.
G-297
C-108 !
T-997
S-873; S-874
C-126; C-127
C-127; C-126
F-233
F-240
B-61; B-59; B-54
B-61 ; H-399
L-491
G-297; F-257
W-1108
W-1102
B-65
S-865
S-865
G-312
G-312
T-997
t r ionea
148
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
C 21 " 2 8 ^ 6
^ 2 1 " 2 8 ̂ 6 * 2
C21H2903Br
C21H2903F
C21H2903N
C21H2904Br
C 2 1 H 2 9 0 4 F
C21H2905C1
NAME OF REACTION PRODUCT
15a, 1 la, 21 - t r ihydr oxy -4 -p regnene -3 ,11 ,20 - t r i one
15j3,17a,21- t r ihydroxy-4-pr egnene - 3 , 1 1 , 2 0 - t r ione
6a, 9a-di f luoro- l l /3 ,16a , 17a, 21 - te t r ahydr oxy-4-pr egnene 3,20-dione
5a, 12a-difluoro-11/3,16a, 17a, 21- te t r ahydr oxy - 4 -pregnene-3 ,20-d ione
17a -bromo -1 l a -hydroxy -4-pregnene-3 ,20-d ione
17a-bromo- l l /3-hydroxy-4-pregnene-3 ,20-d ione
6a - f luoro -17a-hydroxy- l -5a-pregnene-3 ,20-d ione
6a-fluor o -17a -hydroxy-1 -5/3-pregnene-3,20-dione
6a -f l u o r o - 1 l a - h y d r o x y - 4 -pregnene-3 ,20-d ione
12a -aza -C -homo -1 - 5a -p r egnene -3 ,12 ,20 - t r i one
12a -b romo- l l /3 ,16a -dihydr oxy -4 - pr egnene -3,20-dione
6a-f luoro- l l /3 ,16a-dihydroxy-4-pregnene-3 ,20-d ione
6a-fluor o - l l a , 17a-dihydroxy-4-pregnene-3 ,20-d ione
6/3-f luoro-l la , 17a-dihydroxy-4-pregnene-3 ,20-d ione
6/3-fluoro-ll/3,17a-dihydroxy-4-pregnene-3 ,20-d ione
9a-fluor 0-2/3, 11/3-dihydroxy-4-pregnene-3 ,20-d ione
9a-fluoro -11/3,21-dihydroxy-4-pregnene-3 ,20-d ione
12a-f luoro- l l /3 ,14a-d ihydroxy-4-pregnene-3 , 20-dione
12a-f luoro- l l /3 ,16a-d ihydroxy-4-pregnene-3 , 20-dione
6 a - c h l o r o - l l a , 1 7 a , 2 1 -t r ihydroxy-4-pregnene-3 , 20-dione
TRANSFORMATION
15a-OH; 21-OAc-+21-OH
15/3-OH
16a-OH
16a-OH
11a-OH
11/3-OH
Δ1
Δ1
11a-OH
3/3-OAc - 3-C = O; Δ '
16a-OH
16a-OH
11a-OH
11a-OH
11/3-OH
2/3-OH
d , l ^ d - 2 1 - O H + l
14a-OH
16a-OH
11a-OH
YIELD %
-
—
18
—
—
—
—
—
—
26
—
-
—
—
—
—
—
—
—
ORGANISM
Fusa r ium oxysporium
Bacil lus megather ium
Streptomyces roseochromogenus
St reptomyces roseochromogenus
Aspergi l lus ochraceus
Curvular ia lunata
Septomyxa affinis
Septomyxa affinis
Aspergi l lus ochraceus
Ar throbac te r sp .
St reptomyces roseochromogenus
St reptomyces roseochromogenus
Aspergi l lus nidulans
Rhizopus n igr icans
Chaetomella oblonga
Gnomonia f ragar iae
Ophiobolus herpot r ichus
P leospora gaeumanni
Streptomyces roseochromogenus
Aspergi l lus nidulans
CONSTANTS m.p.° [a]D
-
—
242-248
—
—
—
—
—
—
206-207o5
211-212
-
—
—
—
—
—
—
—
-
—
+58[d]
—
-
-
—
—
—
+32[m]
+101[c]
~
—
—
—
—
—
—
—
R E F .
M-599
C-126
M-586
F-261
V-1048; S*835
R-756; R-773
B-34
B-34
V-1048; S-835
M-563
F-256
B-35
F-268
H-391
H-391
L-496
W-1102
W-1103
F - 2 5 6 ; F-257
F-268
149
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C21H2905C1
C 2 1 H 2 9 ° 5 F
C21H2906C1
C 2 1 H 2 9 0 6 F
NAME OF REACTION PRODUCT
6 a - c h l o r o - l l / 3 , 1 7 a , 2 1 -t r i hyd roxy-4 -p regnene -3 , 20-dione
6a- f luoro-2 /3 ,17a ,21-t r ihydroxy-4-p regnene-3 , 20-dione
6a- f luoro- l l /3 ,16« , 17a-t r i hydroxy-4 -p regnene -3 , 20-dione
6 a - f l u o r o - l l a , 17a, 2 1 -t r ihydroxy-4-pregnene-3,20-dione
6a- f luoro-15/3 ,17a ,21-t r ihydroxy-4-pregnene-3 , 20-dione
9 a - f l u o r o - l l / 3 , 1 6 a , 2 1 -t r ihydroxy-4-p regnene-3 , 20-dione
9 a - f l u o r o - l l / 3 , 1 7 a , 2 1 -t r ihydroxy-4-pregnene-3,20-dione
12a -fluor o -11/3,14a, 17a-t r ihydroxy-4-pregnene-3,20-dione
9a -chlor o -2/3,11/3,17a, 2 1 -t e t r ahydroxy-4 -p regnene -3,20-dione
9a -ch lo ro - l l / 3 ,16a , 17a, 2 1 -t e t r ahydroxy-4 -p regnene -3,20-dione
9a- f luoro- l l /3 ,16a , 17aa-t r ihydroxy -17a/3 -hydr oxy -methyl-D-homo - 4 -andr ostene -3 ,17 -dione
9a- f luoro- l l /3 ,16α, 17α, 20/3, 21 -pentahydroxy -1 ,4 -pregnadien-3-one
TRANSFORMATION
11/3-OH; 21-OAc - 21-OH
2/3-OH
16a-OH
11a-OH
15ß-OH
16a-OH
2 1 - C = 0 — 21-OH
21-OAc-> 21-OH
14a-OH
2/3-OH
16a-OH
16a-OH; 17a-OH-17ß-(20-C = 0 - 2 1 - O H ) ^ 17aa-OH-17a/3-CH 2 OH-17-C=0
Δ1
2 0 - C = O ^ 20ß-OH
1
2 0 - C = O — 20/3-OH
YIELD %
-
—
—
32
—
24
~
—
—
—
-
—
< 1
ORGANISM
Cunninghamella bainier i
Gnomonia f ragar iae
St reptomyces roseochromogenus
Aspergi l lus nidulans
Aspergi l lus nidulans
St reptomyces roseochromogenus
St reptomyces roseochromogenus
St reptomyces ol ivochromogenus
P leospora gaeumanni
S t reptomyces roseochromogenus
St reptomyces roseochromogenus
St reptomyces roseochromogenus
Bac te r ium cyclooxydans
Bac te r ium cyclooxydans
Coryne bacter ium s implex
Mycobacter ium rhodochorus
Bac te r ium cyclooxydans
Corynebac ter ium s implex
CONSTANTS m.p.° [α]Ό
-
—
—
201-203
225-228
241.5-244.5
-
—
—
—
252-254
~
—
—
—
262-264
-
—
—
+100[e]
+79 [e]
+127[m]
—
—
—
—
+84[m]
-
—
—
—
-
R E F .
R-770
L-496
M-530
F-268
F-268
H-403
S-907
S-941
W-1103
S-913
S-913
S-910; S-912; G-297; G-295
G-296; G-294
G-296; S-908
G-296; S-908
G-296
S-908
S-908
150
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
^ 21 " 2 9 ^ 6 **
NAME OF REACTION PRODUCT
6a-f luoro- l l /3 ,16α, 1 7 a , 2 1 -te t rahydroxy-4-pregnene-3,20-dione
9a-f luoro- l4 ,11/3 ,17a, 2 1 -te t rahydroxy-4-pregnene-3,20-dione
9a- f luoro-2 /3 , l l j3 ,17a ,21-te t r ahydroxy-4-pregnene-3,20-dione
9a- f luoro-6 j3 , l l /3 ,17a ,21-te t rahydroxy-4-pregnene-3,20-dione
9 a - f l u o r o - 7 a , l l / 3 , 1 7 a , 2 1 -te t rahydroxy-4-pregnene-3,20-dione
9 a - f l u o r o - l l / 3 , 1 4 a , 1 7 a , 2 1 -te t rahydroxy-4-pregnene-3,20-dione
9a-f luoro- l l j3 ,15/3 ,16a ,21-te t rahydroxy-4-pregnene-3,20-dione
9a- f luoro- l lß ,15 j3 ,17a ,21-te t rahydroxy-4-pregnene-3,20-dione
9a - f l uo ro - l l j 3 , 16a ,17a ,21 -te t rahydroxy-4-pregnene-3,20-dione
12a - f luo ro - l l / 3 ,16a ,17a ,21 -te t rahydroxy-4-pregnene-3,20-dione
TRANSFORMATION
16a-OH
1ξ-ΟΗ
Ι ξ - Ο Η ; 21 -OAc-21 -OH
2/3-OH
6/3-OH
6/3-OH; 21 -OAc-21-OH
7a-OH
14a-OH
15/3-OH
15j3-OH
Δ1 - H
16a-OH
16a-OH; 21 -OAc-21-OH
16a-OH
YIELD %
26(cr.)
38
5
2
—
-
—
—
—
—
-
30-70
-
50
-
-
-
ORGANISM
Streptomyces roseochromogenus
Mor t ie re l la sp.
St reptomyces antibioticus
Streptomyces ruber
Streptomyces olivochromogenus
St reptomyces roseochromogenus
St reptomyces r i m o s u s
Streptomyces olivochromogenus
Diplodia na ta lens is
P leospora gaeumanni
Bacil lus mega te r ium
Bacil lus mega te r ium
Bacter ium cyclo-oxydans
Coryne bacter ium s implex
Nocardia i tal ica
Streptomyces californicus
Streptomyces roseochromogenus
Streptomyces sp.
St reptomyces halstedi i
S t reptomyces argenteolus
St reptomyces roseochromogenus
CONSTANTS m . p . ° [α]Ό
234-236
-
248-254
247-252
245-249
224-227
—
—
—
—
-
-
-
250-252
-
235-238
-
+ 95[d]
-
+122[m|
-
+ 1.5[ni|
+ 56[m|
—
—
—
—
-
-
-
+ 97[pl
-
+ 94.5[p]
-
R E F .
M-586; M-533
F-237
F-234
F-234
M-569; S-941
S-912; S-913
S-909
M-569; S-941
T-997
W-1108a
N-669
N-669
G-296
G-296
S-918
L-491
T-1002; G-297; G-295; L-505; S-913
S-788
K-447
H-380
F-256; F-257
151
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C21H2907C1
C21H2907F
^ 2 1 " 3 0 ^ 2
L21 n30U3
NAME OF REACTION PRODUCT
9a-chloro-2/3,11/3,16a, 17a,21-pentahydroxy-4-pregnene-3,20-dione
9a - f luo ro - l£ , 11/3,16o, 17«, 21 -pentahydroxy-4-pregnene-3,20-dione
9a-fluoro-2/3,11/3,16α, 17a,21-pentahydroxy-4-pregnene-3,20-dione
17a -ethyl -17/3-hydr oxy -1 ,4 -andros tadien-3 -one
17/3-hydroxy -1 7a -methyl-16 -méthy lène -4 -andros t en -3 -one
4-pregnene-3 ,20-d ione
17a-ethyl-11/3,17/3-dihydroxy-1,4 -andros tadien-3 -one
17/3 -hydr oxy -4 -androsten -3-one acetate
5 -androstene -3 ,17 -dione 3-ethylene ketal
TRANSFORMATION
2/3-OH
16a-OH
1ξ-ΟΗ
16a-OH
2/3-OH; 16a-OH
1
Δ
3/3-OH -*3-C = 0 ; Δ 5 - Δ 4
3 / 3 - O H - 3 - C = 0 ; Δ 5 - Δ 4
d,l-3/3-OH-> d - 3 - C = 0 + l ; ά , 1 - Δ 5 - α - Δ 4 +1
3/3-OAc-3-C = 0 ; Δ 5 ^ Δ 4
11/3-OH
17ß-Ac-17ß-OAc
17-C=0-*17/3-OAc
17 /3-OH-17-C=0
YIELD %
-
—
3(cr.)
—
24
-
30
-
-
82
-
-
2
—
10-15
-
88
ORGANISM
Streptomyces roseochromogenus
Streptomyces roseochromogenus
Mor t ie re l la zonata
St reptomyces roseochromogenus
St reptomyces roseochromogenus
Corynebacter ium Simplex
Flavobacter ium dehydrogenans
Asper gillus sp0
Bacil lus pulvifaciens
Corynebacter ium helvolum
Eremothec ium ashbyii
Micrococcus dehydrogenans
Pénic i l l ium sp.
Streptomyces sp0
Ustilago zeae
Asper gillus niger
St reptomyces fradiae
Bacil lus pulvifaciens
Curvular ia lunata
Cladosporium r e s i n a e
Saccharomyces fragi l is
Nocardia r e s t r i c t u s
CONSTANTS m . p . ° [α]Ό
-
—
220-223
-
144-146
-
129-130
_
-
127-128
-
-
123-126
125-127
-
-
138.5-140
-
196-198
-
—
- 26.5[m|
—
- 5 [ d |
-
+ 175|d|
-
-
—
-
-
+191
+190
-
-
+ 85 |a |
-
+ 16[c]
REF.
S-913
S-913
F-237
S-912
S-912; S-913
N-667a
B-76
C-104; P-710
T-1027; 1-420
M-546
P-710
E-214
P-710
P-710; P-712; P-716; F-267
P-710
W-1102
W-1102
T-1027; 1-420
N-667a
F-254; F-250
M-572
S-885
152
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
^21 "30^3
NAME OF REACTION PRODUCT
11a, 20/3-dihydroxy -1 ,4 -pr egnadien-3 -one
16a, 20/3-dihydroxy-1,4-pr egnadien-3 -one
16a, 20a -dihydroxy -17/3 -m e t h y l - 1 8 - n o r - 1 7 a - 4 , 1 3 -pr egnadien -3 -one
3,9ξ -dihydroxy - 9 , 1 0 - s e c o -1,3,5(10) -p regna t r i en -20-one
20a-hydroxy-4-pregnene-3,11-dione
1 la -hydroxy-17a-4 -p regnene-3,20-dione
1/3 -hydroxy -4 -pregnene -3,20-dione
1ξ-hydroxy-4-pregnene-3,20-dione
2/3-hydroxy-4-pregnene-3,20-dione
6/3-hydroxy-4-pregnene-3,20-dione
7a-hydroxy-4-pregnene-3,20-dione
7/3 -hydroxy -4 -pregnene -3,20-dione
(Footnote) r ev i s e to 7/3- r e
TRANSFORMATION
1
20-C=O-*20/3-OH
1
20-C=O->20/3-OH
2 0 - C = O ^ 2 0 a - O H ; 13-Me-16a ,17a-oxido->A13-16a-OH-17/3-Me
Δ 1 ; 9a-OH; r ev . aldol. ; enol. ; 9 - C = 0 - 9 ^ - O H
2 0 - C = O - 2 0 a - O H
11a-OH; A 1 6 -17 -Ac-17a -Ac
3 / 3 - O H - 3 - C = 0 ; Δ5 - Δ 4
1|-OH
2/3-OH
6/3-OH
7a-OH
7/3-OH
. T-1037
YIELD %
~
57
—
34
< 1
-
24
-
35
—
t r .
—
-
-
10
—
18
4(cr.)
15
ORGANISM
Bacter ium cyclo-oxydans
Corynebacter ium s implex
Streptomyces lavendulae
Saccharomyces ce rev i s iae
Mycobacterium smegmat i s
Rhodotorula longiss ima
Aspergi l lus niger
Rhizopus n igr icans
Corynebacter ium mediolanum
Flavobacter ium dehydrogenans
Cladosporium sp.
Pénic i l l ium sp.
Mor t ie re l la alpina
Mor t ie re l la pusi l la
Pénic i l l ium ur t icae
Streptomyces aureofaciens
Streptomyces sp.
Çephalosporium sp. (see footnote) Diplodia na ta lens is
Helminthosporium sp.
Phycomyces blakesleeanus
Cladosporium sp.
CONSTANTS m . p . ° [ a ] D
227-229
227-229
226-227
172-175
—
-
209-211.5
153
154-156
-
184-186
:
-
175-176
172-173
—
227-231
229-230
188-191
+ 41[c]
+ 41[c]
- 15[cl
- 15[c]
—
-
- 12[c]
+192[c]
+142[cl
—
-
:
-
+108
+ 98[c]
:
+154[d]
+167[c]
+141[c] +158[d]
R E F .
K-480
T-995
F-288; F -271 ; F-273
C-88; C-90
S-820
C-122
M-603
M-579; M-601; M-605
B-77
N-689
S-941
T-1036
F-239
F-239
E-202
F-288; P-713
S-854; S-847
B-56
T-997
M-570
F-288; F-285; F-286
M-570; S-941
153
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
^21 "30^3
NAME O F REACTION PRODUCT
7/3 -hydroxy -4 -pregnene -3,20-dione
1 lö -hydroxy-4-p regnene-3,20-dione
TRANSFORMATION
7ß-OH
7ß-OH; 3j3-OH->3-C=0; Δ 5 - ^ Δ 4
9ö-OH
l i a - O H
YIELD %
17-36
6-12
31
49
—
—
~
13-17
33
—
-
—
35
—
9
90
15
ORGANISM
Diplodia tuber icola
Diplodia tuber icola
Ascochyta l inicola
Bac te r ium cyclo-oxydans
Circ inel la sp.
Coryne bac te r ium s implex
Mycobacter ium rhodocrous
Nocardia cora l l ina
Nocardia r e s t r i c t u s
Nocardia sp.
Pseudomonas t es tos te ron i
S t rep tomyces aureofaciens
Absidia sp.
Aspergi l lus niger
Asperg i l lus niger
Aspergi l lus ochraceus
Aspergi l lus ochraceus
Aspergi l lus ochraceus
Asperg i l lus sai toi
CONSTANTS m.p.° [a]D
190.5-192.5 +144[d]
— —
191-194 -
190-192 +204[c]
- -
- —
193-194.5 +185
190-191 +188[cl
193-194.5 +185[cl
- -
189-191 +202[cl +150[a]
- -
166-167 +178[c]
— —
165-168 —
- -
168-170 +169[c]
R E F .
T-1023; T-1025; A-28
T-1025; A-28
S-828
S-885
S-815
S-885; P-740
S-885
D-173
S-898; S-885; P-740; S-897
D-172
S-885
P -713 ; F-288
C-98; N-682
F-283
W-1121; W-1120
D-190
W-1067; W-1065
D-193; K-436; M-562; S-797; V-1048; D-182; S-835; S-900; D-181; W-1066; K-454
1-417
9o-hydroxy-4-pregnene-3,20-dione
154
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
^ 2 1 " 3 0 ^ 3
NAME OF REACTION PRODUCT
1 lö -hydroxy-4-pregnene-3,20-dione
TRANSFORMATION
11« -OH
YIELD %
3
-
34
-
-
34(cr.)
—
-
>25
-
—
17
16-28
12
50(cr.)
15
80-83
68-82
50
—
70
ORGANISM
Aspergi l lus sp0
Bacil lus ce reus
Botryt is c ine rea
Cunninghamella echinulata
Cunninghamella sp.
Dactylium dendroides
Gloeosporium kaki
Glomerel la lagenar ium
Pénici l l ium sp0
Pes ta lo t ia foedans
Pes ta lo t ia royenae
Psi locybe cae ru lescens
Rhizopus a r r h i z u s
Rhizopus a r r h i z u s
Rhizopus cambodjae
Rhizopus chinensis
Rhizopus javanicus
Rhizopus n igr icans
Rhizopus n igr icans
Rhizopus n igr icans
Rhizopus n igr icans
Rhizopus sp.
Rhizopus stolonifer
CONSTANTS m.p.° [α]Ώ
161-165
-
165-166
-
-
164-167
-
-
-
-
166-168
166-167
164-165
168.5-169.5
165-167
166-167
166-168
168-170
—
-
-
-
—
-
-
+ 180|c |
-
-
-
-
+ 176 |c |
+176[c]
-
+178[c)
+ 177[c]
+ 180[c]
+176-180[cl
+ 169[c]
—
-
REF.
D-190; M-603; C-104; 1-417; W-1081;l T-1010
M-568
C-98 |
Z-1125
C-98
D-189
S-855
S-855
D-190; C-99
S-882
S-882
C-113 1
P-729
M-601; N-649
C-84
A-29; A-26
N-682
P-729; M-601
T-1028; T-1009; B-42; T-1011
A-26
C-103; R-766; W-1066
M-554; T-1010; A-29; N-682; K-433
T-1011
155
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C2 1 H3 0 O 3
NAME OF REACTION PRODUCT
1 la -hydroxy-4 -p regnene -3,20-dione
1 lß -hydroxy-4-p regnene-3,20-dione
12/3 -hydroxy -4 -pregnene -3 ,20-dione
14a-hydroxy-4-pregnene-3,20-dione
TRANSFORMATION
l l a - O H
d , l - d - l l a - O H + l
3/3-OH^3-C = 0 ; Δ 5 ^ Δ 4 . i i ö _OH
l l ß - O H
12/3-OH
14a-OH
YIELD %
-
—
2
-
-
-
—
-
-
-
-
-
-
-
-
-
-
4
15(cr.)
33
-
3
7-12
—
19
ORGANISM
Sporotr ichum epigaeum
Stachylidium theobromae
Tr i chode rma vi r ide
Tr ichothecium r o s e u m
Rhizopus n igr icans
Aspergi l lus niger
Ps i locybe cae ru l e scens
Absidia sp.
Botryt is c ine rea
Coniothyrium hel lebori
Cunninghamella blakesleeana
Cunninghamella sp.
Curvular ia lunata
Curvular ia lunata
Curvular ia sp„
Pycnospor ium sp.
Coniothyrium hel lebori
Absidia r egn i e r i
Bacil lus c e r e u s
Circ inel la sp .
Cunninghamella blakesleeana
Curvular ia lunata
Curvular ia sp.
Helicostylum pi r i forme
Mucor gr i seocyanus
Mucor gr i seocyanus
Mucor pa ra s i t i cus
CONSTANTS m . p . ° [ a ] D
166-168
-
153-161
-
169-171
-
—
-
-
-
185-187
-
185-188
-
-
192.5-194
191-193
185-188
187-191
190-192
198-200
191-199
180-187
-
195-200
+180[cl
—
-
-
+176[cl
-
:
-
-
-
+214[a]
-
+217[a]
-
—
+197.5[c] +186[e]
+190
+190[c]
—
-
+190[cl
+215[cl
+200[c]
-
+188[c]
R E F .
M-582
V-1048; S-835
W-1119
W-1122
W-1102
F-288
C-113
C-98
C-98
R-749
E-202; C-98
C-98
S-871
C-98; Z-1130
Z-1132
D-147
R-749
T-982
F-288
S-815
N-661
N-661
Z-1132
M-614; E-204
M-614; E-204
S-835; V-1048
M-614; E-204
156
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C 2 J H 3 0 O 3
NAME OF REACTION PRODUCT
14a-hydroxy-4-pregnene-3,20-dione
15a-hydroxy-4-pregnene-3,20-dione
15 j3 - hy dr oxy - 4 -pr e gne ne -3,20-dione
TRANSFORMATION
14a -OH
15a-OH
15/3-OH
YIELD %
24
-
23
24-34
-
-
-
-
-
-
7
-
-
-
7
3
1
—
9
2
18
-
9(cr.)
ORGANISM
Mucor pa ras i t i cus
Mucor pa ras i t i cus
Stachylidium theobromae
Stemphylium botryosum
Colletotr ichum ant i r rh in i
F u s a r i u m lini
Fusa r ium lini
F u s a r i u m lycopers ic i
F u s a r i u m lycopers ic i
Fusa r ium r o s e u m
Fusa r ium sp.
Gibberel la saubinett i
Helminthosporium sat ivum
Hypholoma sp.
Nigrospora oryzae
Nigrospora sp.
Pénic i l l ium notatum
Pénic i l l ium sp„
Pénic i l l ium ur t icae
St reptomyces sp .
Bacil lus mega te r ium
Bacil lus mega te r ium
He 1 mintho sp or iu m sat ivum
Pénic i l l ium sp.
Pénic i l l ium sp.
Phycomyces blakesleeanus
CONSTANTS m . p . ° [ a ] D
184-195
-
187-192
231-232
220-228
230-234
231-232
-
-
-
219-221
228-230
231-232
228-230
-
233-235
231-232
230-234
-
195-199
203-205
202-204
198-202
-
204-205
+200[cl
-
+186[a]
+219
+220[c]
+224[cl
+218[cl
-
-
-
+190[c]
+213[c]
+219
+226[c|
-
+235fe]
+219[c]
+224[c]
-
+158[cl
+155
+149[cl
-
~
+151[cl
R E F .
1-424
N-682
S-835; V-1048
N-661
F-288; F-285; F-287
G-319; T-980
M-599
K-452
S-858
R-747
K-452
S-858
T-1022
M-568; D-191
M-596
M-596
C-86
F-285; F-287
M-576; M-602; E-202
F-285; F-287
H-382
M-568; D-191
T-1022
T-1036
C-99
F-288; F-285; F-286; F-287
157
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
^21 " 3 0 ^ 3
NAME O F REACTION PRODUCT
16a-hydroxy-4-pregnene-3,20-dione
1 la -hydroxy-4-pre gnene-3,20-dione
1 la -hydroxy-4-pr egnene-3,20-dione 17-0 1 8
19-hydroxy-4-pregnene-3,20-dione
21-hydroxy-4-pregnene-3,20-dione (desoxycort icosterone)
TRANSFORMATION
16a-OH
3 /3 -OH^3-C=0 ; Δ 5 _ Δ 4 . 16α-OH
17α-OH
3 / 3 - O H - 3 - C = 0 ; Δ 5 ->Δ 4
17α-ΟΗ(0*8)
19-OH
21-OH
YIELD %
25
—
19
—
-
13
-
—
~
68(cr.)
-
-
50
—
~
-
—
58-77
—
—
ORGANISM
Pes ta lo t i a funera
St reptomyces argenteolus
St reptomyces argenteolus
St reptomyces globosus
St reptomyces ol ivaceus
St reptomyces roseochromogenus
St reptomyces sp.
S t reptomyces sp0
S t reptomyces v i r id i s
St reptomyces argenteolus
Sporormia minima
Tr i chode rma vir ide
Flavobacter ium androstenedionicum
Cephalothecium r o s e u m
Cor t ic ium mic rosc l e ro t i a
Aspergi l lus niger
Cercospore l l a herpot r ichoides
Coniothyrium sp .
Hendersonia rubi
Kabatiel la phoradendr i
Ophiobolus herpo t r ichus
Sclerot inia fructicola
Wojnowicia g ramin i s
CONSTANTS m.p.° [a]D
224-225
225-226
225-226
215-219
225-226
223-225
214-218
223-225
—
210-214
214-215
—
170-171
142-143
—
-
-
-
140-142
-
138-141
+126[c|
+158[c]
+170[c]
+155[c]
+158[c]
+152[c]
+160[c]
+152[c]
—
-
-
—
+175[e]
+185[e]
—
-
-
-
+175
-
—
R E F .
F-266
F-267; P-718
P-716; P-719
V-1060
F-267
F-267
S-847
V-1060; S-847; S-788; L-491
F-267
P-716; F-267
D-182a
M-565; D-185
E-222
H-374
H-350
Z-1123; Z-1124; R-783
L-490
D-186
D-183
L-498
M-584; W-1101; W-1081
W-1101
M-564; D-183; D-184
158
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
^ 2 1 " 3 0 ^ 3
C2 1 H3 0 O4
NAME OF REACTION PRODUCT
21-hydroxy-4-pregnene-3,20-dione
21-hydroxy-4-p regnene-3 ,20-dione 21-O18
X -hydroxy -4 -pr egnene - 3 , 2 0 -dione
20S-lla,20-dihydroxy-4-18,20-cyclopregnen-3-one
16a-hydr oxy-17/3-methyl-18-n o r - 1 3 - δ ξ , 1 7 a - p r e g n e n e -3,20-dione
16/3 - hydr oxy -17/3 - methyl -18 -nor -13 -5ξ ,17a -p regnene -3,20-dione
11a, 17a£-d ihydroxy-17a | -methyl-D-homo - 4 - a n d r o -s tene-3 ,17-d ione
1 7 a , 2 0 a , 2 1 - t r i h y d r o x y - l , 4 -pregnadien-3 -one
17a, 20/3,21-trihydr oxy - 1 , 4 -pregnadien-3 -one
TRANSFORMATION
d,l-*d-21-OH + 1
21-OAc-^21-OH
3/3-OH^3-C = 0 ; Δ 5 - ^ Δ 4
21-OAC-21-OH; 3j3-OH-3-C = 0 ; Δ 5 - Δ 4
Δ4(5ξ-Η)
21 -OHiOf)
X-OH
l i a - O H
3 /3 -OH^3-C=0 ; Δ 5 ->5ξ-Η
3 /3 -OH^3-C=0 ; Δ 5 - 5 ξ - Η
11α-OH; 17a-OH-17/3-Ac — D-homo-17a£-OH-17a£ -Me-17 -C=0
20-C = O ^ 2 0 a - O H
20-C=O-^20/3-OH
1
Δ ; 20-C=O-20j3-OH
YIELD %
—
—
-
34
-
-
-
-
4
63
—
17
25
55
71(cr.)
29
26
25-60
—
-
ORGANISM
Ophiobolus herpot r ichus
Bacil lus mega te r ium
Flavobacter ium sp.
Corynebacter ium mediolanum
Micromonospora chalcea
Pro taminobac te r alboflavum
Pro taminobac te r r u b r u m
Ophiobolus herpot r ichus
Neurospora sitophila
Aspergi l lus ochraceus
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Aspergi l lus niger
Rhodotorula glutinis
Candida pu lche r r ima
Sporotr ichum gougeroti
Alcaligenes sp.
Bacil lus subti l is
Corynebacter ium Simplex
Corynebacter ium s implex
Fusa r ium javanicum
Mycobacter ium flavum
CONSTANTS m.p.° |>]D
140-143
-
-
139-140
-
-
-
~
165-172
205-206
151.5-153
172-173
261-262
212-213
193-195
192-193
190-193
195-196
—
193-194
+180[e]
-
-
—
-
-
-
-
-
+113[dj
+145[dj + 37[cl
+ 93fcl +104[d]
+ 46[c]
+ 13[c"|
+ " M
—
+ 33[m]
—
+ 27[cl
REF.
W-1102
S-948
P-742
M-541; M-544
S-867
S-866
S-866
H-374
M-624
W-1071
S-839
S-839
F-283
T-958
T-958
T-958
S-945
L-522
H-389; N-665
L-522
F-275
C-100
159
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
C21 H30O4
NAME OF REACTION PRODUCT
17a ,20 /3 ,21- t r ihydroxy- l ,4 -pregnadien-3 -one
l l a - h y d r o x y - 1 6 a , 1 7 a - o x i d o -5a -pr egnane -3 ,20 -dione
l l a - h y d r o x y - 1 6 a , 1 7 a - o x i d o -5/3-pr egnane-3 ,20-dione
15a -hydr oxy - 5/3 -pre gnane -3 ,11 ,20 - t r ione
16ö -hydroxy-5/3-pr egnane -3 ,11 ,20 - t r i one
1 la, 20a -dihydroxy -4 -pregnene-3 ,11-d ione
1ξ ,15 | -d ihydroxy-4 -pregnene-3 ,20-d ione
2 β, 15/3 -dihydr oxy -4 -pregnene-3 ,20-d ione
2/3,16a-dihydroxy-4-pregnene-3 ,20-d ione
2/3,17a-dihydroxy-4-pregnene-3 ,20-d ione
2/3,21 -dihydroxy -4 -pregnene -3,20-dione
2/3,X-dihydroxy-4-pregnene-i 3 ,20-dione
TRANSFORMATION
Δ 1 ; 20-C=O->20ß-OH
3 /3 -OAc^3-C=0 ; Δ 5 - + Δ 4 ; Δ1 ; 20 -C=O-20 /3 -OH; 21-OAc^21-OH
11a-OH
11a-OH
15a-OH
16a-OH
2 0 - C = O - 2 0 a - O H
1ξ-ΟΗ; 15ξ-ΟΗ
2/3-OH; 15/3-OH
2/3-OH
2β-ΟΗ; 16α-ΟΗ
2/3-OH
2/3-OH
2β-ΟΗ; Χ-ΟΗ
YIELD %
-
—
—
-
—
-
35
-
60
30-40
24-44
-
19
—
—
1
37(cr.)
-
6
-
3(cr0)
L
ORGANISM
My co bac ter ium lact icola
Pseudomonas boreopolis
Pseudomonas oleovorans
Pseudomonas sp .
S tereum fasciatum
Streptomyces flaveolus
Streptomyces sp0
Corynebacter ium simplex
Aspergi l lus ochraceus
Rhizopus n igr icans
Aspergi l lus ochraceus
Rhizopus n igr icans
Fusa r ium vasinfectum
Sepedonium ampul losporum
Rhodotorula longiss ima
Rhizoctonia solani
Pénic i l l ium sp.
Sclerot inia l iber t iana
Gnomonia f ragar iae
St reptomyces argenteolus
Sclerot inia l iber t iana
Gnomonia f ragar iae
Sclerot inia l iber t iana
CONSTANTS m.p.° [α]Ό
-
-
—
-
-
-
-
205-207
-
170-172
-
220-225
-
217-222
217-219
206-216
215.5-216.5
219-221
196-198
210-216
-
-
—
-
-
-
-
+ 49[c]
-
+ 57[c]
-
-
-
-
51.5[c]
- 67[cl
- 39[c]
-125[c|
22.5[c]
- 65[c]
REF .
S-945
T-960
T-960
N-652; U-1038; U-1039; U-1040
T-959
K-470
K-470
C-115
K-439
K-439
K-440; W-1066
K-440; W-1066
M-599
F-252
C-122
G-312
T-1036
T-983
L-496
P-718; P-716; F-267
T-983
L-496
T-983
160
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C21 H30O4
NAME O F REACTION PRODUCT
6/3,9ö-dihydroxy -4 -pregnene -3,20-dione
6/3, 11α-dihydroxy-4-pregnene-3 ,20-d ione
TRANSFORMATION
6/3-OH; 9a-OH
6/3-OH
6/3-OH; l l a - O H
YIELD %
-
—
—
10
20
30
50-60
3
—
-
-
10
-
-
—
7
30
12
10
< 1
-
ORGANISM
Streptomyces aureofaciens
Aspergi l lus ochraceus
Cunninghamella blakesleeana
Sy ncephalas t r u m r a c e m o s u m
Aspergi l lus niger
Aspergi l lus ochraceus
Aspergi l lus ochraceus
Aspergi l lus ochraceus
Aspergi l lus sai toi
Aspergi l lus sp.
Boletus luteus
Dermoloma sp.
Gloeosporium kaki
Glomerel la lagenar ium
Hygrophorus conicus
Leucopaxillus paradoxus
Rhizopus a r r h i z u s
Rhizopus cambodjae
Rhizopus javanicus
Rhizopus kansho
Rhizopus n igr icans
Rhizopus n igr icans
Rhizopus sp.
CONSTANTS m . p . ° [α]Ό
208-211
—
-
245-247
250-253
-
-
232-234
—
-
-
238-242
-
-
-
245-248
250-254
246-248
232-234
-
-
+ 79[cl
-
-
+152[cl
+100[cl
+100[m]
-
+152[cl
—
-
-
+130[pl
-
-
-
+ 144[pl
+ 155[p] +114[dl
+142[p]
+152[c]
-
-
R E F .
P-714
V-1048
E-202
A-27
F-283
D-190
K-436
D-193; D-181; M-562; S-797; V-1048; D-182; S-900
1-417
1-417; T-1010; D-190
S-825
S-825
S-855
S-855
S-825
S-825
P-729; M-601; M-616
C-84
N-682
A-26
P-729
T-1009
N-682; T-1010
161
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
^ 2 1 "scr-M
NAME OF REACTION PRODUCT
6)3,11a -dihydr oxy - 4 - ι p regnene-3 ,20-d ione
6/3,14a-dihydroxy-4-pregnene-3 ,20-d ione
6/3,15a-dihydr oxy-4 -pregnene-3 ,20-d ione
6/3,16a-dihydr oxy-4-pregnene-3 ,20-d ione
6β, 17α -dihydr oxy -4 -pregnene-3 ,20-d ione
J
TRANSFORMATION
6ß-OH; l l a - O H
3 ß - O H - 3 - C = 0 ; Δ 5 - Δ 4 ; 6/3-ΟΗ; l l a - O H
6/3-OH
6/3-OH; 14α-ΟΗ
15a-OH
6j3-OH; 15a-OH* * (cor rec ted structur<
r e t Ap-18)
6/3-OH
6/3-OH
YIELD
% 1 40
36
-
-
—
-
-
-
14
-
-
-
-
20
-
-
-
-
—
8 - 12β,
-
30
29(cr .
30
ORGANISM
Sclerot ium hydrophilum
Streptomyces sp.
Tr ichoderma sp.
Tr ichothecium r o s e u m
Aspergi l lus niger
Naematoloma subla ter i t ium
Absidia r egn ie r i
Absidia sp„
Achromobacter kashiwasakiens is
Cunninghamella blakesleeana
Cunninghamella elegans
Curvular ia lunata
Curvular ia sp.
Mucor corymbifer
Mucor h iemal is
Mucor mucedo
Naematoloma subla ter i t ium
Trichothecium r o s e u m
Fusa r ium oxysporium
Fusa r ium lini 15a -dihydr oxy -4 -pr eg
Fusa r ium r o s e u m
Aspergi l lus nidulans
Botry t i s c ine rea
F u s a r i u m lycopers ic i
Gibber ella saubinett i
CONSTANTS m.p.° [ e ] p |
236-241
234-240
-
-
—
-
242-246
-
245
246-249
~
-
246-249
255-265
~
-
~
-
-
192-203 kene-3,20
-
230-232
237-240
230-242
+100[m|
+110[ml
-
-
—
—
+132[p] + 114[c]
-
+125[c]
+124[c]
-
-
-
+142[d]
-
-
-
-
-
+130[cl -dione
-
+ 75
+ 15[c]
+ 10[a]
R E F .
S-856
S-854; S-847
T-1010
T-1010
F-288
S-811
T-982
N-682
T-1026
S-811
S-811
S-811
Z-1132
C-82
D-177
S-811
S-811
S-811
M-599
G-319; T-980
R-747
F-267; F-288
S-842
S-858
S-858
162
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
^ 2 1 " 3 0 ^ 4
NAME OF REACTION PRODUCT
6j3,17a-dihydroxy-4-pregnene-3 ,20-dione
6/3,21-dihydroxy-4-pregnene-3 ,20-dione
6/3,21-dihydroxy-4-pregnene-3 ,20 -dione-6/3-Οΐ8
7a, 14a-dihydroxy-4-pregnene-3 ,20-dione
7a, 15j3-dihydroxy-4-pregnene-3 ,20-d ione
7a, 21 -dihydr oxy -4 -pregnene-3 ,20-dione
TRANSFORMATION
6j3-OH
6j3-OH. 17a-OH
6/3-OH
6/3-OH. 21-OAc - 21-OH
21-OH
18 6/3-OH (0 2 )
7a-OH
7a-OH; 14a-OH
7a-OH;15j3-OH
7a-OH
d , l - d - 7 a - O H + l
YIELD %
46
17(cr.)
-
29(cr.)
6
5
1
2-3
34
9
13
8(cr . )
25
—
-
-
-
-
< i
—
-
58
60
-
ORGANISM
Rhizopus a r r h i z u s
Rhizopus n igr icans
Sclerot ium hydrophilum
Naucoria confragosa
Botryt is c inerea
Gibber ella saubinett i
Lenzi tes abietina
Rhizopus a r r h i z u s
Streptomyces fradiae
Streptomyces sp.
Trichothecium ro seum Rhizopus a r rh i zus
Sclerot ium hydrophilum
Aspergi l lus niger
Rhizopus a r r h i z u s
Curvular ia sp.
Curvular ia lunata
Curvular ia lunata
Curvular ia sp.
Mucor hiemal is
Helminthospor ium sat ivum
Cephalosporium sp. *(revise to 7/3 - ref0 Curvular ia sp.
Diplodia na ta lens is
Helminthospor ium sp„
Pez i za sp.
Pez iza sp .
CONSTANTS m . p . ° [α]Ό
244-246
256-258
238-240
-
198-205
-
190-192
181-183
198-202
198-202; 206-210 (solvate)
190-198
198-200
-
252-255
280
252-255
234-238
250-253
T-1037)
-
216-225
216-226
-
+6[cj
+4[cl
+8[cl
-
+96fc]
-
-
+110[el
+115[cl
+97[c]
+97[cl
+105[m|
—
—
+175[cl
+177[m]
+175[c]
-
+121[ml
-
+144[c]
+158
+155
R E F .
M-580
M - 6 0 1 ; M-607
S-856
S-825
S-842
U-1043
M-585
M-601
H-328
S-847
M-584
E-203
S-856
Z-1124; Z-1123; R-783
H-374
S-813
Z-1130; Z-1132
D-187
S-813
D-177
T-1022
B-56
M-585
T-997
M-570
M-585
W-1102
163
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
^ 2 1 " 3 0 ^ 4
NAME OF REACTION PRODUCT
7/3, 14a-dihydroxy-4-pregnene-3 ,20-d ione (revised s t ruc tu re - ref. T-1037)
7/3,15/3-dihydroxy-4-pregnene-3 ,20-d ione
7/3,21-dihydroxy-4-pregnene-3 ,20-d ione
9a, 14a-dihydroxy-4-pregnene-3 ,20-d ione
9a ,15a-dihydfoxy-4 -p regnene-3 ,20 -dione
9a, 17a - dihydr oxy - 4 -pregnene-3 ,20-d ione
9a ,21-d ihydroxy-4-pregnene-3 ,20-d ione
TRANSFORMATION
7/3-OH; 14a-OH
15/3-OH
7/3-OH ;15j3-OH
3/3-OH-3-C = 0 · Δ5 - Δ4; 7/3-OH; ' 15/3-OH
7/3-OH
9a-OH
14a-OH
9a-OH; 14a-OH
15a-OH
9a-OH
9a-OH
9a-OH; 21-OAc - 21-OH
YIELD %
5
6
8
1
5
10
19-25
21-42
32
3
44
10
-
—
10-20
7(cr.)
-
10
44
t r .
1
ORGANISM
Absidia r egn ie r i
Diplodia tuber icola
Diplodia tuber icola
Diplodia tuber icola
Diplodia tuber icola
Helminthosporium sat ivum
Pénic i l l ium sp.
Syncephalast rum r a c e m o s u m
Diplodia tuber icola
Cladiosporium sp.
Circinel la sp.
Circinel la sp.
Absidia r egn ie r i (assignment of
s t ruc tu re is doubtful )
Circ inel la sp.
Calonectr ia decora
Nocardia sp.
Mucor pa ras i t i cus
Neurospora c r a s s a
Nocardia sp.
Nocardia sp.
Pseudomonas t e s tos te ron i
Ascochyta linicola
Helicostylum pi r i forme
Mucor pa ras i t i cus
CONSTANTS m.p.° [α]Ό
208-214
231-233
231-232
231-233
231-232
230-232
232-234
225-226
178-181.5
—
249-253d
272-273
240-242
—
182-184
182-184
180-182
-
-
187-188
180-183
+154[cl
+136|c |
+122[c|
+136|c |
+122|c |
+130[c|
+122[c|
+122[c|
+151|c |
—
+149[c|
+179[c]
+212[cj
—
+167[c]
+163[c]
+168[c]
-
-
-
+167[cl
R E F .
T-982
T-1025
A-28
T-1025
A-28
T-1022
T-1036; T-1037J D-177 Ί
T-1020; A-26; A-27'
T-1025; A-28
M-570
S-815
S-815
T-982
S-815
S-810
D-173
S-937
S-937
S-796
D-173
S-898; P-740
S-828
E-204
E-204; M-640
164
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
C21H30O4
NAME OF REACTION PRODUCT
11a, 15a-dihydroxy-4-pregnene-3 ,20-d ione
11a, 15/3-dihydroxy-4-pregnene-3 ,20-d ione
11a, 16a-dihydroxy-4-pregnene-3 ,20-d ione
1 l a , 17a -dihydroxy -4 -pregnene-3 ,20-d ione
11a, 18-dihydroxy-4-pregnene-3 ,20-d ione
TRANSFORMATION
15a-OH
11a-OH; 15/3-OH
11a-OH
11a-OH
17a-OH
11a-OH; 17a-OH
11a-OH
YIELD %
—
6(c r . )
*(revis 42(cr.)
15
-
41
22
-
30(cr.)
—
2
75
ca. 14
21(cr.)
—
27
6
8-15
—
—
ORGANISM
Calonectr ia decora
Gibberel la zeae
Aspergi l lus giganteus
Nigrospora oryzae le to 12/T-OH; Γ5α-ΟΗ
Aspergi l lus niger
Aspergi l lus niger
Aspergi l lus niger
Aspergi l lus ochraceus
Absidia r egn ie r i
Cunninghamella echinulata
Dactylium dendroides
Gloeosporium kaki
Glomerel la lagenar ium
Rhizopus a r r h i z u s
Rhizopus n igr icans
Sclerot inia l iber t iana
Sclerot ium hydrophilum
Dactylium dendroides
Sepedonium ampul losporum
Aspergi l lus sp .
Cephalothecium r o s e u m
Dactylium dendroides
Tr ichothecium r o s e u m Aspergi l lus ochraceus
Rhizopus n igr icans
CONSTANTS m . p . ° [α]Ό
182-183
173-175
+180[ml
+134[c]
202-203 +134ÎC1 - ref0 Ap-18) L ' 213-215
219-221
-
216-221
215-217
-
219-222
—
220-223
220-222
218-221
214-224
—
210-214
218-222
224-227; 248-251
195-197
~"~
+128[c]
+87[cl
—
+80[c]
—
—
+80[c]
—
-
+76[c]
+73[cl
+80[c]
—
—
+74[c]
+74[m]
—
-
R E F .
S-814
M-599
D-179; D-180
M-596
F-267; F-283
F-283
M-603
V-1048; S-835
S-841
Z-1125
D-189
S-855
S-855
M-601
M-580; M-601; M-607; H-391
T-983
S-856
D-189
M-646
D-190
M-600
D-189; D-188
T-1010
W-1110
W-1100
165
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
1 C21H30O4
NAME OF REACTION PRODUCT
l l a , 2 1 - d i h y d r o x y - 4 -pregnene-3 ,20-d ione
l l a , 2 1 - d i h y d r o x y - 4 -pr e gnene -3 ,20 -dione -l lö -Oie
11/3,14a-dihydroxy-4-pregnene-3 ,20-d ione
TRANSFORMATION
11a-OH
11a-OH; 21-OAc - 21-OH
21-OH
11a-OH; 21-OH
3/3-OH-*3-C = 0 ; Δ5 - Δ4; 11a-OH; 21-OH
11a-OH (O")
11/3-OH; 14a-OH
YIELD %
67
-
28
-
-
40
-
17
16
-
6
65
9(cr.)
28
-
-
—
-
—
—
—
ORGANISM
Aspergi l lus niger
Aspergi l lus niger
Aspergi l lus ochraceus
Coniothyrium helleborine
Cunninghamella echinulata
Dactylium dendroides
Gloeosporium kaki
Glomerel la lagenar ium
Rhizopus sp„
St reptomyces sp.
Aspergi l lus nidulans
Aspergi l lus us tus
Rhizopus a r r h i z u s
Rhizopus n igr icans
Sclerot ium hydrophilum
Aspergi l lus niger
Hendersonia a b e r r a n s
Wojnowicia graminis
Aspergi l lus niger
Psi locybe cae ru le scens
Psi locybe cae ru le scens
Rhizopus n igr icans
Curvular ia lunata
Curvular ia lunata
CONSTANTS m.p.° [a]D
153-154
-
150-152
-
-
153-161
158-159
153-156
153-158
-
154-158
153-155
156-160
147-150
-
—
153-154
-
—
—
224-229
+168[c]
-
—
-
-
+180[m]
+171[e]
+165[c]
+166[c;
-
~
+166[c] +165[e]
+173[m]
—
~
—
+163[e]
-
—
—
+211[m]
R E F .
F-283 1
M-603
D-193 ; D-182; V-1048; S-835
T-1003
Z-1125
D-189
S-855
S-855
K-433
S-847
M-603
M-603
E-203
E - 2 0 3 ; M-601
S-856
Z-1124; Z-1123
D-183
D-183; D-184
W-1121; W-1120; W-1081
C-113
C-113
H-374
D-187
Z-1130
166
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
C 2 1 H 3 0 ° 4
NAME OF REACTION PRODUCT
11/3,14a-dihydroxy-4-pregnene-3 ,20-d ione
11/3,15a-dihydroxy-4-pregnene-3 ,20-dione
l l ß , 17a-dihydroxy-4-pregnene-3 ,20-dione
l l /3 ,21-dihydroxy-4-pregnene-3 ,20-d ione (cort icosterone)
l l /3 ,21-dihydroxy-4-p regnene-3 ,20-d ione-11/3-018
12/3,14a-dihydroxy-4-pregnene-3 ,20-d ione
TRANSFORMATION
11/3-OH; 14a-OH
15a-OH
11/3-OH
17a-OH
11/3-OH
21-OH
11/3-OH; 21-OH
d , l - » d - l l ß - O H + 1
11/3-OH (O28)
12/3-OH
YIELD
% 1 _
-
32
—
-
-
— —
~
29
—
28
-—
10(cr . )
—
19
~
— -
-
-
—
ORGANISM
Curvular ia sp.
Calonectr ia decora
Curvular ia lunata
Rhodoseptoria sp.
Spondylocladium aus t r a l e
Stachylidium theobromae
Cephalothecium r o s e u m
Sporormia minima Tr ichoderma vir ide
Colletotr ichum sp.
Coniothyrium helleborine
Cort ic ium sasak i i
Cunninghamella blakesleeana Curvular ia lunata
Pycnospor ium sp.
Rhodoseptoria sp.
Stachylidium bicolor
Tr ichothecium r o s e u m
Aspergi l lus niger
Coniothyrium sp.
Hendersonia acicola
Wojnowicia graminis
Curvular ia lunata
Curvular ia lunata
Cunninghamella blakesleeana
Calonectr ia decora
CONSTANTS m.p.° [ e ] p |
224-227
173-175
226-228
-
-
~
— —
-
178-180
—
178-180
-—
177-179
—
179-182
-
— -
-
178-181
—
240-242
J
+219[m]
+230[c]
+135.5[a]
-
-
-
— —
-
+216[e]
—
+210.5[e]
-—
+220[el
—
—
-
--
~
+220[e]
—
+129[c]
R E F .
Z-1132
S-817
S-871
K-446
H-391
D-146
M-600
D-182a D-185
T-1003
T-1003
H-350
M-555
S-871; S-875 D-147
K-446 S-843
T-1003
Z-1124; Z-1123; R-783 D-186
D-183
D-184
R-783
W-1102
H-374
S-810
167
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
^21 "30^4
NAME O F REACTION PRODUCT
12ß, 15α -dihy dr oxy -4 -p regnene-3 ,20-d ione
12ß, 15α -dihydroxy -4 -p regnene -3 ,20 -d ione -1 l a 12a-H3
12/3,15a-dihydroxy-4-pr eg -nene-3 ,20-dione-12/3 ,15a-O 1 8
14a, 15β-dihydroxy-4-pregnene-3 ,20-d ione
14a, 21-dihydroxy-4-pregnene-3 ,20-d ione
15a, 21-dihydroxy-4-pregnene-3 ,20-d ione
TRANSFORMATION
12/3-OH
12/3 -OH; 15a-OH
3 / 3 - O H - 3 - C = 0 Δ 5 - * Δ 4 ; 12/3-OH; 15a-OH
12β-ΟΗ; 15a-OH
12β-ΟΗ; 15α-ΟΗ(Οχ
28)
14a-OH; 15/3-OH
14a-OH
14a-OH; 2 1 - O A C - 2 1 - O H
21-OH
d , l - » d - 1 4 a - O H + 1
15a-OH
YIELD %
—
77
10
—
—
1
—
32
44(cr„ )
-
36(cr„ )
17
26
—
-
—
83-87
-
81
20-70
ORGANISM
Calonectr ia decora
Calonectr ia decora
(cor rec ted structurels 15/3-diol ent r ies)
Calonect r ia decora
Calonectr ia decora
Calonectr ia decora
Helminthosporium sat ivum
Cunninghamella b lakes leeana
Mucor pa ras i t i cus
Mucor pa ras i t i cus
Stachylidium bicolor
Absidia r egn ie r i
Helicostylum p i r i forme
Mucor gr iseocyanus
Mycobacter ium smegmat i s
Aspergi l lus niger
P leospora gaeumanni
Fusa r ium lini
Fusa r ium lycopers ic i
Fusa r ium oxysporum
Gibberel la bacca ta
CONSTANTS m . p . ° [o?]D
— —
218 +139[c] +186[m]
; - see 6/3,15a-diol a
— —
— —
259-263 +136[mj
__ —
174-179 —
166-169
172-177 —
170-175 +171[c]
167-17305 —
175-176 +190[c] (solvate) 167-170o5 (unsolvated)
— —
— —
_ —
198-214 +202.5[c)
- -
222-227 +212[c]
216-222 +196[e]
REF .
S-814
S-814; G-319; M-596*
id 11a,
S-816
H-370
K-485
T-1022
M-555
E-204
T-980
S-843
S-841
E-204
E-204;
S-873
Z-1123
W-1102
G-319; T-980; W-1074
S-858
M-599
M-585; U-1043
168
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C2 1 H3 0 O4
NAME OF REACTION PRODUCT
15a, 21 -dihydroxy -4 -pregnene-3 ,20-dione
15/3, 17α-dihydroxy-4-pregnene-3 ,20-dione
15/3, 21 -dihydroxy-4 -pregnene-3 ,20-d ione
16a, 21 -dihydroxy - 4 -pregnene-3 ,20-dione
17a, 21-dihydroxy-4-pregnene-3 ,20-d ione (Reicnstein's Compound S)
TRANSFORMATION
15a-OH
15a-OH; 21-OAc - 21-OH
d , l - d -15a -OH+l
15/3-OH
15/3-OH
d , l — d -15ß-OH+l
16a-OH
16a-OH; 21-OAc — 21-OH
d, 1 - d - 1 6 a - O H + l
17a-OH
21-OH
YIELD %
25
50
—
-
—
-
—
2
10(cr.)
19
-
—
—
-
15
4
-
-
—
27(cr. )
17
-
—
—
~~~
ORGANISM
Gibberella saubinett i
Gibberel la saubinett i
Gibberel la zeae
Pénic i l l ium notatum
Nigrospora oryzae
Gibberel la baccata
Nigrospora oryzae
Sclerot inia l iber t iana
Botryt is c inerea
Lenzi tes abietina
Lenzi tes abietina
Streptomyces argenteolus
Streptomyces roseochromogenus
Streptomyces sp0
St reptomyces sp.
Streptomyces argenteolus
Streptomyces californicus
St reptomyces sp.
Sporormia minima
Tr ichoderma vir ide
Tr ichothecium r o s e u m
Aspergi l lus niger
Coniothyrium sp .
Hendersonia phragmi t i s
Ophiobolus herpot r ichus
Wojnowicia graminis
CONSTANTS m.p.° [α]Ό
215-220
~
-
215-220
210-213
-
213-215
258-259d
202-209
206-216
—
201-203
-
203-205
202-203
-
-
__
202-213
204-207
-
—
—
"~"
+217[c]
-
-
+186[e]
+214[c]
+195
+74[c]
+54[c]
+147[c]
+141.5
+141
—
+129[c]
-
+114.5[e]
+130[c]
~
+144
—
+132[c]
-
-
—
—
" * ■"
R E F .
S-858
U-1043
M-599
C-86
M-596
W-1102
M-596
T-983
S-842
M-585
W-1102
F-288
F-288; F-267
F-267
V-1054
F-267
L-491
W-1102
D-182a
D-185
M-584
Z-1124; R-783
D-186
D-183
M-584; W-1101
D-184
169
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C21H30O4
C21 H30 O5
NAME OF REACTION PRODUCT
Reichstem' s Compound S
19,21-dihydroxy-4-pregnene-3,20-dione
3/3, lla-dihydroxy-5-pregnene-7,20-dione
3/3, lla-dihydroxy-16a, 17a-oxido-5-pregnen-20-one
Products of unknown or questionable structure
11/3,17a, 20/3,21-tetrahydroxy -1,4-pr egnadien-3-one
12/3,17a, 20/3,21-tetr ahydroxy-1,4-pr egnadien-3-one
TRANSFORMATION
21-OAC-21-OH
3/3-OHr 3-C = 0 ; Δ5 - Δ4
3/3-OH-> 3 - C = 0 ; Δ5 — Δ4 ; 21-OAc-,21-OH
3/3-OAc-> 3-C = 0 ; Δ5 — Δ4 · 21-OAc — 21-OH
3/3-OH^ 3- C = 0 ; Δ5 - Δ4 ; 20/3-OH — 20-C=O
19-OH
11a-OH; 7 - C=0
11a-OH
Substrate Progesterone
desoxycorticosterone 21- acetate
20-C = O^20/3-OH
20-C=O-^ 20/3-OH
YIELD %
—
—
87
93
—
—
18
-
,,
-
10
5
0.5
0.2
0.3
0.5
0.3
1
26(cr.)
4(cr.)
-
ORGANISM
Bacillus megaterium
Flavobacterium sp.
Flavobacterium dehydrogenans
Flavobacterium dehydrogenans
Acetobacter suboxydans
Corticium microsclerotia
Rhizopus arrhizus
Fusarium solani
Myrothecium roridum
Absidia regnieri
Absidia regnieri
Curvularia sp.
Mucor corymbifer
Mucor corymbifer
Mucor corymbifer
Mucor corymbifer
Mucor corymbifer
Mucor corymbifer
Mucor corymbifer
Pénicillium sp.
Sclerotinia libertiana
Sclerotinia libertiana
Mucor parasiticus
Streptomyces griseus
Corynebacterium simplex
CONSTANTS m.p.° [a]D
—
—
208-210
209
—
153-156
228-230
-
212-213.5
227-228.5
~
270-275
218-223
275-280
217-220
240-250
275-280
210-215
251-253
216-224
228-238d
180-197; 200-225
-
245-247
-
—
+110[c]
+110[c]
—
—
—
-
+154[e]
+88[p]
-
-
-
-
-
-
-
~
+202
-18[P]
+190[c]
+152[c]
-
REF.
S-948
P-742
H-378
H-378
L-523
H-350
E-202-M-630; M-601 Ί
P-746
P-746
T-982
T-982
Z-1132
C-82
C-82
C-82
C-82
C-82
C-82
C-82
F-285; F-287
T-983
T-983
T-980
C-110
R-749
170
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C2 1 H3 0 O5
NAME OF REACTION PRODUCT
17a,21-dihydroxy-5/3-pregnane -3 ,11 ,20 - t r ione
11/3,17a, 20/3,21 - tetrahydroxy-1,4 -pr egnadien -3 -one
1 Ία, 20a, 21 - t r ihydroxy -4 -p regnene-3 ,11 -dione
17a,20/3,21-tr ihydroxy-4-pregnene-3 ,11-d ione
1 la, 2 0 | , 21 - tr ihydroxy - 4 -pregnene-3 ,11-d ione
l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
2/3,11/3,21 - tr ihydroxy - 4 -pregnene-3 ,20-d ione
2/3,15/3,21 - t r ihydroxy - 4 -pregnene-3 ,20-dione
2β, 17a, 21- t r ihydroxy-4-p r e gnene-3,20-dione
TRANSFORMATION
Δ 4 ^ 5 / 3 - Η
20-C=O^20/3-OH
1 Δ ;
20-C=O->20/3-OH
2 0 - C = O ^ 2 0 a - O H
20-C=O^20/3-OH
2 0 - C = O - 2 0 4 - O H
1/3-OH
l ß -OAc^ l /3 -OH; 21 -OAc^21-OH; 3/3-OAc-»3-C=0; Δ 5 ^ Δ 4
2/3-OH
2/3 -OH; 15/3-OH; 21-OAc^21-OH
2/3-OH
YIELD %
~
95
—
32
;
-
-
-
-
57
50(cr.)
68
40-60
5
-
68
19(cr.)
20(cr.)
< 1
35
< 1
ORGANISM
Al te rnar ia bataticola
Streptomyces albus
St reptomyces hydrogenans
St reptomyces sp.
Rhodotorula longiss ima
Calonectr ia decora
Fusa r ium solani
Fusa r ium sp.
Gloeosporium ol ivarum
Hydrogenomonas facil is
Mycobacter ium sp.
St reptomyces albus
St reptomyces g r i seus
St reptomyces hydrogenans
Rhizobium sp.
Rhizoctonia ferrugena
Rhizoctonia sp.
F lavobacter ium dehydrogenans
Sclerotinia l iber t iana
Sclerot inia l iber t iana
Conidiobolus sp.
Gnomonia f ragar iae
Helminthosporium t r i t ic i -vulgar i s
Rhizoctonia ferrugena
CONSTANTS m.p.° [a]D
214-217
-
-
240-242d
—
-
-
-
-
202.5-205.5
206-207
190; 204
-
193-207d
-
203-207
183-186
210-219
232-235
208-213
225.5-228d
+ 92
-
-
+158[dl
—
-
-
-
-
+137[dl
-
-
-
+ 89[d]
—
-7[m]
- 47[ml
- 88[el
- 59[d]
- 58[d]
R E F .
S-852
K-459
L-522
K-470
C-110; C-122
S-951
S-949
S-951
K-465
F-228
S-917
K-459
C-110
L-522
C-114
G-315; G-312; G-313
S-793b; G-313
N-689
S-840; S-853
S-849; S-853
W-1073
L-496
K-460
G-313
171
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA j
CaiH,0O5
!
NAME OF REACTION PRODUCT
2/3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
6/3,11a, 21 - tr ihydroxy - 4 -pregnene-3 ,20-d ione
6/3,11/3, 21- t r ihydroxy-4-pregnene-3 ,20-d ione
6/3,17a, 21 - t r ihydroxy - 4 -pregnene-3 ,20-d ione
TRANSFORMATION
2/3-OH
2/3-OH; 21-OAc-*21-OH
6/3-OH; l l a - O H ; 21-OAC-21-OH
6/3-OH
11/3-OH
6ß-OH
YIELD %
3
-
~
-
6
—
19(cr.)
1
3
33
4-6
30
5(cr.)
—
-
-
-
-
35-40
-
-
-
-
39
26
-
1 -
ORGANISM
Rhizoctonia ferrugena
Rhizoctonia sp.
Sclerot inia l iber t iana
Sclerot inia sc l e ro t io rum
Streptomyces sp0
S t reptomyces argenteolus
Sclerot ium hydrophilum
Trichothecium r o s e u m
Curvular ia lunata
Absidia spc
Achromobacter kashiwasakiens is
Ar throbot rys super ba
Bacil lus ce r eus
Botryt is c inerea
Coniothyrium hellebori
j Cor iolus vers ico lor
Cor t ic ium sasak i i
Cunninghamella blakesleeana
Cunninghamella sp.
Curvular ia lunata
Curvular ia sp0
F u s a r i u m d imerum
F u s a r i u m lycopers ic i
F u s a r i u m r o s e u m
Gibberel la saubinett i
Gibberel la saubinett i
Gloeosporium foliicolum
Glomer ella cingulata
CONSTANTS m.p.° [a]D
220-222
209-211
215-222
-
22505-228
224-227
220-226
225-227
225-227
224-226
-
222
228-235
-
-
223
-
-
229-232
-
228-232
-
—
230-236
1 -
-
-
—
-
- 64[d]
-
- 58fd]
—
+105[ml
+118jdl
+ 118[dj
+ 60.5[e]
-
+ 58[m]
+ 42[c]
-
-
-
-
-
+ 57[e]
-
+ 55[d]
-
-
+ 72[ni|
-
-
-
R E F .
G-315; G-312
G-312
S-860; T-983
S-860
H-383
P-716; F-267
S-856
N-654
N-654
N-682
T-1026
E-226
S-944
S-842
R-749
B-63
H-327
S-919
C-98; N-682
K-469
K-469
K-462
S-858
R-747
S-858
U-1043
K-464
K-464
172
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
C 2 1 H 3 0 O 5
NAME OF REACTION PRODUCT
6/3,17a,21-tr ihydroxy-4-pregnene-3 ,20-d ione
7a ,14a ,21 - t r ihydroxy-4 -pregnene-3 ,20-d ione
7a, 17a, 21 - t r ihy dr oxy -4 -pregnene-3 ,20-d ione
TRANSFORMATION
6/3-OH
6/3-OH; 17a-OH
6/3-OH; 17a-OH; 21-OAc - 21-OH
7a-OH
7a-OH; 14a-OH
7a-OH
YIELD %
2
—
-
-
-
—
-
-
-
-
30
3
-
-
24 (cr.)
30
35-40
40
36
-
< 1
20
24
19
> 3 0
ORGANISM
Helicostylum pi r i forme
Helminthosporium l ee r s i i
Mucor sp.
Pe l l i cu la r ia fi lamentosa
Phoma sp.
Polyporus tulipiferus
Po r i a cocos
Rhizoctonia solani
Rhizoctonia solani
Rhizoctonia sp.
Rhizopus a r r h i z u s
Rhizopus n igr icans
Rhizopus sp.
Scenedesmus sp.
Sclerot ium hydrophilum
Streptomyces sp.
Streptomyces sp.
Vert ic i l l ium malthousi
Vert ic i l l ium niveos t ra tosum
Cephalothecium r o s e u m
Cephalothecium ro seum
Mucor gr iseocyanus
Mucor gr iseocyanus
Diplodia nata lens is
Diplodia tuber icola
CONSTANTS m . p . ° [o?]p
228-232
225-231
-
219-221
-
-
-
233-234
-
-
230-233
230-234
-
-
231-238
230-235
-
230-233
-
234-236
—
245-248
248-240
228-230
-
+55[d|
-
-
-
-
-
+67[aj
-
-
+58.5|e]
-
-
-
+62|cj
+51 [m]
-
+57[e]
-
+53
—
+146[dl
+97[e]
+146[m]
REF .
E-204 . M-60l '
K-460
N-682
T-957
1-422
B-63
B-63
T-956
S-793b
G-312
P -725 · M-601; Μ-βΙδ '
P - 7 2 5 ; M-615*
N-682
L-527
S-856
S-854; S-847
C-112
K-468
K-468
M-581
M-600
C-94
C-94
T-997; T-999; T-998
T-1023; A-28
173
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
C2 1 H3 0 O5
NAME OF REACTION PRODUCT
7/3,14a, 15/3-trihydroxy-4-pregnene-3 ,20-d ione
7/3 ,17a,21- t r ihydroxy-4-pregnene-3 ,20-d ione
7^ ,17a ,21 - t r ihydroxy-4 -pregnene-3 ,20-d ione
8 j3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
9 a , l l | 3 , 2 1 - t r i h y d r o x y - 4 -pregnene-3 ,20-d ione
9a, 17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
11a, 17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
TRANSFORMATION
14a-OH
7/3 -OH; 14a-OH; 15/3-OH
7/3-OH
7 | -OH
8/3-OH
9a-OH
9a-OH
11a-OH
1
YIELD %
38(cr.)
8
5
—
16(cr. )
-
-
—
10
10
60(cr. )
8-15
10
-
21
-
37
44
70
—
4 0 - 5 0
70
25
—
ORGANISM
Syncephalas t rum r a c e m o s u m
Absidia r e g n i e r i
Syncephalas t rum r a c e m o s u m
Syncephalast rum sp.
Cephalosporium a s p e r u m
Cephalosporium sp.
Pénic i l l ium sp.
Rhizoctonia sp.
Cercospora melonis
Ascochyta l inicola
Ascochyta linicola
Curvular ia lunata
Helicostylum pi r i forme
Nocardia aurant ia
Nocardia coral l ina
Nocardia r e s t r i c t u s
St reptomyces aureofaciens
Absidia glauca
Absidia orchid is
Absidia r egn ie r i
Absidia sp.
Ar throbot rys superba
Aspergi l lus nidulans
Aspergi l lus niger
Aspergi l lus niger
CONSTANTS m . p . ° [α]Ό
-
267-269
263-265
263-265
—
209-211
-
-
219-223
—
235-240
231-235
248-252
-
-
236-238
218-220
205-209
206-209
—
-
-
217-219
—
-
+75[pl
+103[mj
+170[ml
—
+94[ml
-
-
+109[dl
—
+103[d]
+107[dl
-
-
+103[d]
+120[e]
+110[cl
+120[ml
—
-
-
+117[el
—
R E F .
T-1021
T-982
T-1021; A-27
A-26
B-56
B-56; B-55
T-1037; T-1036
G-312
K-472
S-828
S-828
K-469
E-204; M-601; M-609
S-898; P-740
D-173
P-740
P - 7 1 5
N-682
H-334
S-841
N-682; C-98; S-801
E-226
F-288
F-283
M-603
174
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
C21H30O5
NAME OF REACTION PRODUCT
l l û , 1 7 û , 2 1 - t r i h y d r o x y - 4 -pregnene-3 ,20-dione
TRANSFORMATION
l l a - O H
YIELD %
60-85
50
28
88
> 7 0
-
-
-
2
-
-
3
-
13(cr.)
88
30
-
—
3-5
-
-
30
70(cr.)
—
ORGANISM
Aspergi l lus ochraceus
Aspergi l lus ochraceus
Aspergi l lus sp.
Bacil lus ce reus
Beauveria sp.
Cercospora melongenae
Cercospora sc i rpicola
Cercospora zinniae
Colletotr ichum sp.
Conidiobolus sp .
Coniothyrium hellebor ine
Conocybe si l igenoides
Cort ic ium sasaki i
Cort ic ium sasaki i
Cort ic ium vagum
Coryneum cardinale
Cunninghamella echinulata
Cunninghamella echinulata
Cunninghamella sp.
Curvular ia lunata
Curvular ia sp.
Dactylium dendroides
Didymella lycopers ic i
Fusa r ium equiset i
Fusa r ium sp .
CONSTANTS m . p . ° [α]Ώ
-
-
203-209
212-214
215-218
211-216
-
-
206-209
-
—
212-216
-
212-216
219-220
216-217
-
-
213-215
-
-
210-212
210-213
—
-
-
+110[ml
-
+120[el
—
-
-
+82[ml
-
-
+120[e]
-
+120[e]
—
-
-
-
+120[e]
-
—
—
+117[el
—
R E F .
K-436
D-193; D-182; V-1048; S-835
D-190
S-944
1-421
K-472
K-472
K-472
T-1003
W-1073
T-1003; T-1004
C-113
H-325
H-347
H-350
T-991
Z-1125
K-466
N-682
K-469; K-443
K-469
D-189
S-836; S-835; V-1048
M-557
M-557
175
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
^ 2 1 " 3 0 ^ 5
NAME OF REACTION PRODUCT
11a, 17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
TRANSFORMATION
l la-OH
YIELD %
—
38
88
49
—
tr.
> 7 0
-
-
-
-
—
55
30
-
—
-
23 (cr.)
61
15
—
11
-
27
ORGANISM
Gloeosporium foliicolum
Gloeosporium kaki
Glomerel la cingulata
Glomerel la lagenar ium
Glomerel la sp.
Helicostylum p i r i forme
Helminthosporium sigmoideum
Mucor sp„
Pe l l i cu la r i a f i lamentosa
Phoma sp.
Psi locybe sp .
Rhizoctonia sp.
Rhizopus nigr icans
Rhizopus sp.
Rhizopus sp.
Sclerotinia l iber t iana
Sclerot inia sc l e ro t io rum
Sclerot ium hydrophilum
Sporotr ichum sulfurescens
Stachylidium bicolor
Stachylidium theobromae
St reptomyces sp.
St rophar ia cubensis
Sycephala s t r u m r a c e m o s u m
CONSTANTS m.p.° [α]Ό
214-218 +120rej
204-208 + 115fej
212-214 —
200-209 +110[mj
- -
206-211 —
210-213 +120jej
- -
210-212 +112[dl
- -
- -— —
209-212; +113[c] 217-219 +113[mj (polymorphs)
207-211 +115[e]
- -
205-209 +115[el
- -
205-210 +112fml
205-210 -
- -
- -
205-210 +117|m!
- -
208-210 +107lc|
REF.
K-464
S-859; S-855
C-109
S-855
C-109; K-464
E-204; M-601
K-460
N-682
T-957
1-422
C-113
G-313; G-312; S-793b
P-725 ; M-601; M-641
K-433
N-682
S-860
S-860
S-856
M-582
K-468
D-146
S-854; S-847
C-113
A-27
176
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C21 H30 O5
NAME OF REACTION PRODUCT
lla,17a,21-trihydroxy-4-Pregnene-3,20-dione
l lß , 12ß, 15a-trihydroxy-4-pregnene-3,20-dione
l lß , 14α, 17ö-trihydroxy-4-pregnene-3,20-dione
llß,14a,21-trihydroxy-4-pregnene-3,20-dione
llß,15a,21-trihydroxy-4-pregnene-3,20-dione
llß,15ß,21-trihydroxy-4-pr egnene -3,20 -dione
l lß , 16a,21-trihydroxy-4-pregnene-3,20-dione
llß,17a,21-trihydroxy-4-pregnene-3,20-dione (hydrocortisone)
TRANSFORMATION
11a-OH
11a-OH; 21-OAc -*21 -OH
11a-OH; 17a-OH
21-OAc^ 21-OH; lla-OH; 17a-OH
12ß-OH; 15a-OH
llß-OH; 14a-OH
llß-OH
15a-OH
15ß-OH
16a-OH
llß-OH
YIELD %
—
9
—
—
—
—
1
—
caQ 20
37
—
20
—
—
—
—
6-8
33(cr0)
2(cre)
—
19
—
—
—
ORGANISM
Trichothecium roseum
Verticillium theobromae
Coryneum cardinale
Rhizopus nigricans
Cephalothecium roseum
Dactylium dendroides
Trichothecium roseum
Calonectria decora
Curvularia lunata
Stachylidium bicolor
Fusarium moniliforme
Botrytis cinerea
Sclerotinia libertiana
Streptomyces roseochromogenus
Absidia glauca
Absidia orchidis
Absidia sp.
Arthrobotrys superba
Botrytis cinerea
Botrytis cinerea
Botrytis cinerea
Botrytis fabae
Botrytis peoniae
Cercospora zinniae
Chaetomella oblonga
CONSTANTS m.p.° [a]D
-
213-215
—
—
206-211
—
—
229-231
247-250
206-215
—
235-244
230-235
—
206-210
—
—
213-216
201-209
—
200-208
—
207-210
—
—
+120[e]
—
—
+121[m]
—
—
+148[c]
+181[e]
+180[m]
—
+180[p]
+180[p]
—
+163[e]
—
—
+162[e]
+156[m]
—
+155[e]
—
+160[e]
—
REF.
T-1003; M-600
K-468
T-991
M-601; M-641
M-581
D-189; D-188
M-600
S-817
S-876
S-841; S-843; S-851
M-599
S-842
S-853; S-840
H-399
N-682
H-334; N-682
S-801; C-98
E-226
F-229
S-842
C-98
S-859
F-229
K-472
S-789
177
TABLE I
T r a n s f o r m a t i o n s by Product
I EMPIRICAL FORMULA
C2 1 H3 0 O5
NAME OF REACTION PRODUCT
hydrocortisone
TRANSFORMATION
11/3-OH
YIELD %
—
—
—
—
—
37
19
65
5-20
—
—
39
40-55
—
—
—
—
—
<10
ORGANISM
Chaetomella raphigera
Colletotrichum sp0
Coniothyrium hellebori(ne)
Corticium microsclerotium
Corticium practicola
Corticium sasakii
Corticium vagum
Cunninghamella blakesleeana
Cunninghamella blakesleeana
Cunninghemella blakesleeana
Cunninghamella sp.
Curvularia falcata
Curvularia lunata
Curvularia lunata
Curvularia lunata
Curvularia lunata
Curvularia pallescens
Dothichiza ferruginosa
Epicoccum sp.
Helminthosporium sigmoideum
Pellicularia filamentosa
Phoma sp.
CONSTANTS ™.p.° [β ] ρ |
— —
— —
205-207 +162[e]
— — — —
205-207 —
208-210 +160[a]
— —
— —
— —
208. 5-20a 5+166[e]
— —
212-215d +160[e]
— —
— —
— ■ —
208-212 +160[e]
204-207 +178[e]
REF.
S-789
T-1003
T-1003; T-1004; T-993; F-288; R-749
H-350
H-350
H-350; H-347; H-325
H-350
H-339
M-556
M-601; M-641; M-555; 0-696; S-919
C-98
S-878
S-871; S-875
K-443; K-466
K-469
D-192; C-98
S-875
,K-449
R-782
K-460
T-957
1-422
178
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C 2 i H 3 0 O 5
NAME OF REACTION PRODUCT
hydrocort isone
TRANSFORMATION
llj3-OH
d , l ^ d - l l / 3 - O H + l
llj3-OH; 21-OAc-»21-OH
17a-OH
YIELD %
—
—
—
—
—
—
— ·
20(cro;
—
46
50(cro)
—
—
—
1
5-10
—
28
—
—
—
—
—
—
ORGANISM
Pseudomonas boreopolis
Pseudomonas spD
Pycnospor ium sp0
Rhizoctonia sp.
Rhodoseptor ia sp„
Sclerot inia l iber t iana
Sclerot inia sc l e ro t io rum
Spondylocladium aus t r a l e
Spondylocladium xylogenum
Stachylidium bicolor
Stachylidium bicolor
Stachylidium bicolor
Stachylidium theobromae
Stachylidium theobromae
Streptomyces fradiae
Streptomyces fradiae
Tr ichothecium r o s e u m
Vert ic i l l ium theobromae
Curvular ia lunata
Botry t i s c ine rea
Cort ic ium mic ros l e ro t ium
Curvular ia lunata
Stachylidium theobromae
Cephalothecium r o s e u m
CONSTANTS m.p.° [e]D
—
—
—
—~
—
201-206
—
—
—
—
202-208
—
201
—
202-204
—
—
210-213
209-212
—
—
—
—
—
—
—
—
—
—
+160[e]
—
—
—
—
+162[m]
—
+163[c]
—
+16405[e]
-
—
+160[e]
+171[e]
—
—
—
—
—
R E F .
T-960
N-652; U-1038
D-147
G-312; G-313; S-793b
K-446
S-860
S-860
S-790
S-790
K-468
S-843
D-146
D-146
S-835
C-134; C-135; H-328
C-112
S-878; T-1003
K-468
W-1102
F-229
H-3&)
Z-1131
D-146
M-600
179
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
^ 2 1 ^ 3 0 ^ 5
NAME OF REACTION PRODUCT
hydrocort isone
11/3,18, 21- t r ihydroxy-4-pregnene-3 ,20-d ione
l l / 3 ,19 ,21 - t r i hyd roxy-4 -pregnene-3 ,20-d ione
12/3 ,17a,21- t r ihydroxy-4-pregnene-3 ,20-d ione
14a ,15a ,21 - t r i hyd roxy-4 -pregnene-3 ,20-d ione
14a ,17a ,21 - t r i hyd roxy-4 -pregnene-3 ,20-d ione
TRANSFORMATION
17a-OH
21-OH
Δ Α - Η
2 1 - O A c ^ 2 1 - O H
11/3-OAc-» 11/3-OH; 21-OAc-*21-OH
Δ4 (5/3-H)
11/3-OH
d , l - » d -21 -OH+l
11/3-OH
12/3-OH
15a-OH
14a-OH
YIELD %
—
—
—
—
—
2
—
90
—
—
—
21
7
25
29
—
—
—
—
15-20
—
—
3-6
—
—
—
—
ORGANISM
Sporormia minima
Trichothecium r o s e u m
Coniothyrium sp.
Hendersonia herpot r icha
Wojnowicia graminis
Baci l lus mega te r ium
Cunninghamella elegans
Flavobacter ium dehydrogenans
Nocardia a s t é ro ïdes
Cunninghamella blakesleeana
Ophiobolus herpot r ichus
Cunninghamella b lakes leeana
Curvular ia lunata
Coniothyrium hel lebori
Fusa r ium lini
Absidia r egn i e r i
Coriolus ve r s i co lo r
Cunninghamella b lakes leeana
Curvular ia lunata
Curvular ia lunata
Curvular ia lunata
Curvular ia sp .
Helicostylum p i r i forme
Helminthosporium avenae
Mucor sp.
P o r i a cocos
Polyporus tul ipiferus
CONSTANTS m.p.° [<*]D|
—
202-210
—
—
—
210-215
—
—
—
—
—
163-164
—
179-181
208-222
213-218
—
—
229-233d
227-230
—
—
.234-237
227-230
—
—
—
—
—
—
—
—
—
—
—
—
—
—
+210[c]
—
—
+172[c]
+155[mj
—
—
+147[d]
+150[d]
—
—
+155[m]
+148[m]
—
—
—
REF.
D-182a
M-584
D-186
D-183
D-184
H-382
E-225
C-129
S-939
W-1100
W-1102
B-40
N-654
R-749
T-980
S-841
B-63
E-202; S-919
K-469
K-469
K-443
K-469
E-204; M-601
K-460
N-682
B-63
B-63
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C21 H30°5
NAME OF REACTION PRODUCT
14α , 17a, 21- t r ihydroxy-4-pregnene-3 ,20-d ione
15a, 17a, 21 -tr ihy dr oxy -4 -pregnene-3 ,20-dione
15/3,17a, 21- t r ihydroxy-4-pregnene-3 ,20-d ione
16a, 17a, 21- t r ihydroxy-4-pregnene-3 ,20-d ione
17a, 19 ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
TRANSFORMATION
14a-OH
14a-OH; 21-OAc-+21-OH
15a-OH
15a-OH; 2 1 - O A c - 2 1 - O H
15/3-OH
16a-OH
16a-OH; 2 1 - O A c - 2 1 - O H
19-OH
YIELD %
5 ( c r 0 )
—
—
2-4
5
42(cr . )
29(cr . )
—
3
15
50
—
2
—
—
—
15(cr„)
30-70
—
—
—
42
3
8 ( c r J
ORGANISM
Stemphylium botryosum
Mycobacter ium smegmat i s
Calonectr ia decora
Fusa r ium r o s e u m
Gibberel la baccata
Gibberel la saubinett i
Helminthosporium sat ivum
Hormodendrum olivaceum
Rhizoctonia sp.
Fusa r ium Uni
Aspergi l lus niger (our ass ignment - que Baci l lus mega te r ium
Coriolus vers ico lor
Pénic i l l ium sp.
Phoma sp0
P o r i a cocos
Polyporus tulipiferus Spicaria s impl i c i s s ima
Nocardia i tal ica
Pes ta lo t ia funarea
Streptomyces roseochromogenus
Streptomyces v i r id is
Streptomyces californicus
Cort ic ium mic rosc le ro t ium Cort ic ium sasak i i
Cort ic ium vagum
CONSTANTS m . p . ° [α]Ό
227-228d
226-228
225-227
—
—
216-218
227-230
—
176-178
248-250 stionable)
+144[m]
+130[a]
+146[m)
-
-
+145[mj
+146[m]
-
+146[mj
+97[e]
218-220d; +103[e] 240-241d (polymorphs)
—
219-222
—
—
—
240-242
—
—
—
—
235-236
233-236d
233-236
-
+88[e]
—
—
—
+96[m]
—
—
—
—
+121[e] +123[e| +127[d] +144[e]
+143[e] + 128[d]
R E F .
N-661
S-873
S-810
R-747
U-1043
U-1043
T-1024
ß - 5 8 ; A-9
G-312
T-980
F-283
H-382; C-127; C-126
B-63
T-1036
1-422
B-63
B-63
B-58; A-9
S-918
S-835
H-399; V-1048; S-835
V-1048; S-835
L-491
H-350
H-325; H-326; H-347 H-350
TABLE I 180
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
181
EMPIRICAL FORMULA
C2 1 H3 0 O5
^ Ι ^ ο ^ β
NAME OF REACTION PRODUCT
17a ,19 ,21 - t r i hyd roxy-4 -pregnene-3 ,20-d ione
X , 1 7 a , 2 1 - t r i h y d r o x y - 4 -p regnene ,3 ,20 -d ione
11a, 16a, 17aa- t r ihydroxy-17a/3-hydroxy methy l -D-homo-4 -andr ostene - 3 , 1 7 -dione
11/3,16a, 17aa- t r ihydroxy-17a/3-hydroxymethyl-D-homo -4 -andr ostene - 3 , 1 7 -dione
1ξ, 11/3,17α, 21- te t rahydroxy-4-pregnene-3 ,20-d ione
6/3,11/3,17a, 21- te t rahydroxy -4 -pregnene-3 ,20-d ione
6/3,14a, 17a ,21- te t rahydroxy-4-pregnene-3 ,20-d ione
7a, 11/3,17a, 21- te t rahydroxy-4-pregnene-3 ,20-d ione
7α, 14α, 17a ,21- te t rahydroxy-4-pregnene-3 ,20-d ione
11α, 16α, 17a,21- te t rahydroxy-4-pregnene-3 ,20-d ione
11/3,14a, 17a, 21- te t rahydroxy-4-pregnene-3 ,20-d ione
11a, 15/3,17a,21-tetrahydroxy-4-pregnene-3 ,20-d ione
TRANSFORMATION
19-OH
19-OH; 21-OAc - 21-OH
X-OH
16a-OH; 16a,17a-diOH-17/3 (-20-C=O-21-OH) -D-homo-16a, 17aa-diOH-17a/3-CH2OH-1 7 - C = 0
16a-OH; 16a,17a-diOH-17/3 (-20-C = O - 2 1 - O H ) -D-homo-16a, 17aa-diOH-17a/3-CH2OH-1 7 - C = 0
1 | -OH
6/3-OH
6/3-OH; 11/3-OH
6β-ΟΗ
14α-OH; 6β-ΟΗ
7α-OH
7α-OH; 11/3-OH
7α-OH
7α-OH; 14α-OH
16α-OH
11/3-OH; 14a-OH
15/3-OH
YIELD %
33
-
—
17(cr.)
-
10
5
-
-
40
5
-
—
—
-
-
ORGANISM
Hypochnus sasaki i
Pe l l i cu la r i a f i lamentosa
Cor t ic ium mic rosc l e ro t ium
Sclerot inia l iber t iana
St reptomyces roseochromogenus
St reptomyces roseochromogenus
St reptomyces antibioticus
Mor t ie re l l a sp .
S t reptomyces sp.
Curvular ia lunata
Curvula r ia lunata
Curvular ia sp.
Diplodia na ta lens is
Curvular ia lunata
Curvular ia lunata
Curvular ia lunata
Curvular ia lunata
Curvular ia sp .
S t reptomyces roseochromogenus
Curvu la r ia lunata
Curvula r ia lunata
Curvula r ia lunata
Baci l lus mega te r ium
CONSTANTS m.p.° [a]D
234-235
-
219-225d
210-212.5
-
216-220d
-
-
231-234d
238-240d
-
-
241-242
232-233 solvate
-
+123[e"|
-
-
+136[m]
-
+87[d]
-
-
+146[d]
+48[c]
-
-
+183[e] +152[d]
+188[e]
-
R E F .
S-869
T-957
H-350
T-983
G-297
G-297
F-234
F-239
C-112
K-469
K-469
K-469
T-997
K-443
K-469
K-469
S-879
K-469
G-297
A-2 S-877
S-877 S-879
K-443
C-126
182
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
^21 "30^6
(^21H31(-)5F
C 2 1 H 3 1 0 6 F
C2 1n32W2
NAME OF REACTION PRODUCT
11/3,15β,17α, 21 -tetrahydroxy-4-pregnene-3 ,20-d ione
11/3,16a, 17a ,21 - te t rahydr oxy-4-pregnene-3 ,20-d ione
11 β, 17α, 19,21 - te t rahydr oxy-4-pregnene-3 ,20-d ione
X, 11 β, 15α, 21 - te t rahydr oxy-4-pregnene-3 ,20-d ione (X is 8/3,9a or 14a)
Unknown
9a- f luoro- l l /3 ,17a , 20/3,21 -t e t rahydroxy-4-pregnene-3-one
9a-f luoro- l l /3 ,16a , 17a, 20/3, 21-pentahydroxy-4-pregnen-3-one
5a-pregnane-3 ,20-d ione
TRANSFORMATION
11/3-OH
15/3-OH
16a-OH
19-OH
X-OH; 15a-OH
Substrate proges te rone
20 -C=O-20 /3 -OH
20-C = O --+ 20/3-OH; 21-C = 0-+ 21-OH
20-C=O — 20/3-OH; 21-OAc - 21-OH
Δ ' - Η
20-C=O-> 20/3-OH
Δ1 — H; 20-C=O - 20/3-OH
16a-OH; 20-C=O^20/3-OH
Δ4 -> 5a-H
YIELD %
-
30-70
—
29
2
-
—
-
—
—
—
-
—
—
—
-
ca. 30
—
ORGANISM
Curvular ia lunata
Bacillus Megater ium
Nocardia i tal ica
Strep to my ce s roseochromogenus
Hypochnus sasak i i
Fusa r ium lycopers ic i
Gibberel la saubinetti
Mucor corymbifer
St reptomyces roseochromogenus
Streptomyces roseochromogenus
Streptomyces olivochromo genus
Bacter ium cyclooxydans
Corynebacter ium simplex
Bac te r ium cyclooxydans
Corynebacter ium simplex
Mycobacter ium rhodochorus
Bac te r ium cyclooxydans
Corynebacter ium simplex
Mycobacter ium rhodochorus
Streptomyces roseochromogenus
Cor t inar ius evernius
Mycobacter ium smegmat i s
Ophiobolus herpot r ichus
CONSTANTS m.p.° [α]Ό
- -
- -
- -
180-182 +216[m]
225 —
- -
- -
- -
_ _
- -
— —
- -
132-145; +49.5[ml 227-231d (hydrate )
— —
— —
■ - -
197-200 —
— —
REF.
C-126
C-127; C-126
S-918
G-297; H-399
S-870
S-858
S-858
C-82
S-907
S-907
M-569; S-941
G-296
G-296
G-296
G-296; S-908
G-296
G-296
G-296; S-908
G-296
S-907
S-825
S-820
W-1081
183
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
^ 2 l " 3 2 ^ 2
1 ^ 2 l " 3 2 ^ 3
NAME OF REACTION PRODUCT
5a-pregnane-3 ,20-d ione
5ß-pregnane-3 ,20-dione
20a-hydroxy-4-pregnen-3-one
20ß-hydroxy-4-pregnen-3-one
17a-ethyl-17/3,19-dihydroxy-4-andros ten-3-one
5-androstene-3/3,17/3-diol-3-acetate
3/3,16a, 20a- t r ihydroxy-17ß-m e t h y l - 1 8 - n o r - 1 7 a - 5 , 1 3 -pregnadiene
1 l a -hydroxy-5a -p regnane -3,20-dione
1 la-hydroxy-5/3-pr egnane-3,20-dione
1 la -hydroxy-5ß-pregnane-3 ,20-dione-12a-H 3
15a-hydroxy-5a-pregnane-3,20-dione
15a-hydroxy-5ξ-pregnane-3,20-dione
16a -hydr oxy- 5/3-pr egnane -3,20-dione
TRANSFORMATION
Δ4 — 5a-H
Δ — 5ß-H
5 4 Δ - > Δ ; 3/3-OH ■--» 3 - C = 0
20-C=O * 20a-OH
20-C=O > 20/3-OH
19-OH
17-C = 0 - 17β-ΟΗ
16a, 17a-oxide -» 16a-OH ; 13/3-CH3 — 17ß-CH3; 20-C = O — 20a-OH ; Δ13
11a-OH
11a-OH; Δ4 - 5a-H
11a-OH
l l a - H 3 -» 11a-OH
15a-OH
15a-OH; Δ4 - 5 | - H
16a-OH; Δ4 -» 5/3-H
YIELD %
9
-
-
87
> 3 9
—
2
-
—
67
71
20(cr.) - 6 0
26
t r .
40
-
—
-
t r . -8
ORGANISM
Pénici l l ium ur t icae
Streptomyces g r i seus
Alter na r i a bataticola
Bacil lus putr if icus
Fla vo bac te r ium dehydrogenans
Rhodotorula longiss ima
Pénici l l ium li lacinum
Streptomyces lavendulae
Hypochnus sasaki i
Saccharomyces ce rev i s iae
Tr ichomonas gallinae
Saccharomyces ce rev i s iae
Rhizopus n igr icans
Rhizopus nigr icans
Aspergi l lus niger
Rhizopus n igr icans
Sporotr ichum epigaeum
Rhizopus n igr icans
F u s a r i u m sulphureum
F u s a r i u m lini
St reptomyces argenteolus
CONSTANTS m . p . ° [α]Ό
185-198
204-206
120-122
119-120
—
—
151-152
170-172
—
146
-
202-204
197-200
198-200
102-106
-
123-125
-
219-229
199-200
—
-
+ 124
-
—
—
-
+81[c]
-
-
-
-189[e]
+82[c]
+84[c]
+83[cl
—
—
-
+8405[cl
+90.5[c|
REF .
M-602 1
V-1059; W-1097
S-852
M-545
N-693
C-122
M-637; S-832
F -284 ; F-271
S-869
M-539
S-829 ; S-830
C-88 ; C-90
E-209 ; M-601
P-729
M-603
E-209; M-601
M-582
H-371
M-599
G-319; T-980
P - 7 1 8 ; P - 7 1 6 ; F-267
184
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C-2l"32^3
NAME OF REACTION PRODUCT
21 -hydroxy-5a-pregnane-3,20-dione
21-hydr oxy-5/3-pr egnane -3,20-dione
3a-hydroxy-5a-pregnane-11,20-dione
3a-hydr oxy-5/3-pr egnane-11,20-dione
6/3, l l a -d ihydroxy-3a , 5a-çyçlopregnan-20-one
6/3, l l /3-dihydroxy-3a, 5a-cyclopregnan-20-one
11a, 20a-dihydroxy-4-pregnen-3-one
11a, 20/3-dihydr oxy-4-pregnen-3-one
11/3,20a-dihydr oxy-4-pregnen-3-one
16a, 20/3-dihydroxy-4-pregnen-3-one
17a, 20a -dihydr oxy -4 -pregnen-3-one
2 0/3,21-dihydr oxy-4-pre gnen-3-one
(revision of s t ruc tu re at 2 0 - see réf. S-832)
3/3, 7/3-dihydroxy-5-pregnen-20-one
3/3, l l a -d ihydroxy-5 -p regnen-20-one
3/3,21-dihydroxy-5-pregnen-20-one
3/3, 16a-d ihydroxy-5a-9( l l ) -pregnen-20-one
TRANSFORMATION
Δ 4 ^ 5 α - Η
Δ4 - 5/3-H
3 - C = 0 - 3a-OH
3-C = 0 - 3a-OH
11a-OH
11/3 -OH
11a-OH
20-C=O - 20a-OH
11a-OH
20-C=O - 20/3-OH
2 0 - C = O - 20a-OH
20-C=O - 20/3-OH
20-C = O — 20a-OH
20-C=O -» 20/3-OH
2 0 - C = O ^ 20/3-OH; 21-OAc - 21-OH '
7/3-OH
11a-OH
21-OH
16a-OH; 3/3-OAc - 3/3-OH
YIELD %
-
-
40-44
60
-
16
82-85
2
-
-
-
—
-
—
—
14
—
ORGANISM
Streptomyces gr i seus
Alter nar ia bataticola
Saccharomyces cerev is iae
Saccharomyces ce rev i s iae
Aspergi l lus ochraceus
Metar rh iz ium anisopliae
Rhizopus n igr icans
Curvular ia lunata
Rhizopus n igr icans
Rhodotorula longiss ima
Rhizopus nigr icans
Pénic i l l ium li lacinum
Rhodotorula longiss ima
Streptomyces lavendulae
Rhodotorula longiss ima
Pénici l l ium sp.
Streptomyces sp.
Pénic i l l ium sp.
Rhizopus n igr icans
Metar rh iz ium anisopliae
Aspergi l lus niger
Streptomyces sp.
CONSTANTS m.p.° [a]D
162-164
-
160-165
169-171
-
208-212
211.5-217
243.5-249.5
-
178-179
-
212-213
-
-
—
181-183
—
-
-
+93[cl
+103[c]
-
-
+92[c]
—
-
+73[c]
-
+44[c)
-
-
—
—
—
REF.
V-1059; W-1097
S-852
C-83; C-89
C-83; C-89
S-835
K-483
W-1069; W-1070
W-1070
S-832
C-122
S-832
S-832
C-122
F-271 ; F-273; F-288
C-122
M-637
E-202
M-637
E-202
K-483
R-783
W-1092
185
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
j C a i H 3 2 0 3
C21H3204
NAME OF REACTION PRODUCT
16a, 20a-dihydroxy-17/3-methy l -18-nor - 5/3,17a-13-pregnen-3-one
11a ,15a-d ihydroxy-5a-pregnane-3 ,20-d ione
11a, 15a -dihydr oxy -5/3 -p regnane-3 ,20-d ione
l l /3,21-dihydroxy-5/3-pregnane-3 ,20-d ione
12/3,15a-dihydr oxy-5a-pregnane-3 ,20-d ione
12/3,15a-dihydroxy-5/3-pregnane-3 ,20-d ione
15a, 21-dihydroxy-5/3-pregnane-3 ,20-d ione
16a, 21 -dihydroxy-5/3-pregnane-3 ,20-d ione
17a,21 - dihydroxy-5a -pregnane-3 ,20-d ione
17a, 21 - dihydr oxy - 5/3 -p regnane-3 ,20-d ione
3/3,16a - dihydr oxy -5a-pregnane-11 ,20-d ione
6/3,15£,20ξ - t r ihydroxy-4-pregnen-3-one
11/3,17a,20a-tr ihydroxy-4-pregnen-3-one
17a, 20a, 21 - t r ihydr oxy -4 -pregnen-3-one
17a,20/3 ,21- t r ihydroxy-4-pregnen-3-one
TRANSFORMATION
16a, 17a-oxido —* 16a-OH; 13j3-CH3 - 17/3-CH3; 20-C=O - 20a-OH; Δ13
15a-OH
15a-OH
Δ 4 - 5/3-H
12j3-OH; 15a-OH
12/3-OH; 15a-OH
15a-OH; 21-OAc -» 21-OH
16a-OH; 21-OAc -> 21-OH; Δ4->5/3-Η Δ4 - 5a-H
Δ4 - 5/3-H
16a-OH
6β-ΟΗ; 15ξ -OH; 2 0 - C = O - 20 4 -OH
2 0 - C = O - 20a-OH
20-C=O -» 20a-OH
20-C=O - 20/3-OH
YIELD %
20
60
40
—
40
40
—
—
—
—
—
—
40
-
65(cr.)
27(cr.)
—
—
62(cr.)
-
-
-
ORGANISM
Saccharomyces ce rev i s iae
Calonectr ia decora
Calonectr ia decora
Al te rnar ia bataticola
Calonectr ia decora
Calonectr ia decora
Fusa r ium oxysporium
Streptomyces argenteolus
Streptomyces g r i seus
Al te rna r ia bataticola
Pes ta lo t ia funera
Rhizoctonia solani
Rhodotorula glutinis
Rhodotorula longiss ima
Rhodotorula glutinis
Rhodotorula longiss ima
Rhodotorula longiss ima
Bacil lus sp.
Bacil lus subti l is
Candida pu l che r r ima
Chlorel la sp.
Corynebacter ium s implex
Demat iacea sp.
CONSTANTS m . p . ° [ a ] D
223-225
208-210
175-177
—
253-257
225-231
—
215-217
—
185-190
—
237-240
209-210
—
220-222
221-225
—
—
188-190
-
-
-
-58[e]
+105[cl
+108.5 [cj
—
+70 [m]
+56[cl
—
+44[cl
—
+40
—
+70[dl
+94[cl
—
+60[el
+55[dl
—
—
+77[cl
-
-
-
R E F .
C-88; C-90
S-816
S-816
S-852
S-816
S-816
M-599
F-267
V-1059
S-852
W-1092
G-312
T-958
C-122
T-958
C-110
C-122
V-1045
L-522
T-958
V-1045
L-522
V-1045
186
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C21 H32°4
^21 "32^5
NAME OF REACTION PRODUCT
17a,20/3,21-tr ihydroxy-4-pregnen-3-one
17a ,20£ ,21- t r ihydroxy-4-pregnen-3-one
3/3, 7/3, l l a - t r i h y d r o x y - 5 -pregnen-20-one
Unknown
l l a ,17a ,21 - t r i hydroxy-5 /3 -pregnane-3 ,20-d ione
l l /3 ,17a,21- t r ihydroxy-5/3-pregnane-3 ,20-d ione
3/3 ,17a,21- t r ihydroxy-5a-p r e g n a n e - l l , 2 0 - d i o n e
TRANSFORMATION
2 0 - C = O - 20/3-OH
d , l - 2 0 - C = O -d-20/3-OH + 1
20-C=O ^ 20ξ -OH
7ß-OH ; 11a-OH
Substrate
desoxycor t icosterone
desoxycor t icosterone acetate
l l a - O H
11a-OH; Δ4 - 5/3-H
Δ4-> 5/3-H
3-C = 0 - 3/3-OH; Δ4 — 5a-H
YIELD %
5
—
—
32
-
—
-
54
64
-
—
48
-
-
-
40-60
18
6(cr.)
12
8 (c r . )
-
17
ORGANISM
Didymella lycopers ic i
Diplodia tuber icola Epicoccum sp.
Hydrogenomonas facilis
Pénic i l l ium ci t r inum
Pénici l l ium li lacinum
Pseudomonas f luorescens
Pythium ult imum
Streptomyces albus
Streptomyces dias ta t icus
Streptomyces hydrogenans
Streptomyces lavendulae
Streptomyces sp.
St reptomyces sp.
Streptomyces coelicolor
St reptomyces lavendulae
Rhizobium sp.
Rhizopus a r r h i z u s
Mucor pa ras i t i cus
Rhizopus n igr icans
Rhizopus n igr icans
Al te rnar ia bataticola
Catena bacter ium sp.
CONSTANTS m . p . ° [ot]O
189-190
-
-
172-177
-
—
-
191-193
188-189
183. I 9 4 '
-
175. 19θ '
-
193-194
-
-
247-248
196-206
218-222
190-196
192-198
195-200
—
-
-
+71[d |
-
—
-
+65[d|
+65.5fd|
-
-
+65[d]
-
+74[e]
-
-
-41[m|
+121[c|
+57M
+94
—
REF.
V-1048; S-836; S-835 A-28
R-782
F-228
S-846
M-637
N-652 . T - 9 6 0 ' U-1030
S-846
K-458
K-470
L-522
S-835
C-110
K-470
W-1094
W-1094
C-114
M-601-E - 2 0 2 '
T-980
P-725
P-725 ; M-606
S-852
T-973
187
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
^21 "32^5
C 2 1 H 3 3 ° 4 F
1 ^ 2 l " 3 4 ^ 2
NAME OF REACTION PRODUCT
3a, 17a, 21- t r ihydr oxy - 5/3-p regnane-11 ,20-d ione
l l a , 1 7 a , 2 0 a , 2 1 - t e t r a -hydroxy-4-pregnen-3-one
11a, 17a, 20/3,21 - t e t r a -hydroxy -4 -pregnen-3-one
11/3,17a, 20a, 21 - t e t r a -hydroxy-4-pregnen-3-one
11/3,17a, 20/3,21-tetra-hydroxy-4-pregnen-3-one
11/3,17α, 20έ, 2 1 - t e t r a -hydroxy-4-pregnen-3-one
17a, 19,20a, 21 - tetrahydroxy -4-pregnen-3-one
X ,17a ,21 - t r ihydroxy-5 f -pregnane-3 ,20-d ione (X probably is l l a -OH)
9 a - f l u o r o - 3 ß , l l ß , 1 6 a -t r ihydroxy-5a-pregnan-20-one
3a -hydroxy-5a-pregnan-20-one
3/3-hydroxy-5a-pregnan-20-one
TRANSFORMATION
3 - C = 0 ^ 3 a - O H ; Δ*-»5/3-Η
2 0 - C = O - 2 0 a - O H
2 0 - C = O - 2 0 ß - O H
11/3-OH
2 0 - C = O - 2 0 a - O H
20-C=O->20ß-OH
2 0 - C = O - 2 0 £ - O H
19-OH
20-C=O-*20a-OH
X-OH; Δ 4 - ^ 5 ξ - Η
16a-OH
3 - C = 0 - > 3 a - O H ; Δ 4 - 5 α - Η
3-C=0-»3ß-OH
YIELD %
56
< 1
-
74
5
—
—
—
-
59
—
16(cr.)
80
-
40-60
10
—
—
—
-
ORGANISM
Al te rna r ia batat icola
Clost r id ium paraput r i f icum
Streptomyces sp.
Rhodotorula longiss ima
Streptomyces hydrogenans
Pe l l i cu la r i a f i lamentosa
Rhodotorula longiss ima
Hydrogenomonas facil is
Mycobacter ium smegmat i s
Pe l l i cu la r i a f i lamentosa
St reptomyces a lbus
St reptomyces d ias ta t icus
St reptomyces g r i seus
St reptomyces hydrogenans
St reptomyces sp.
Rhizobium sp .
Pe l l i cu l a r i a f i lamentosa
Rhodotorula glutinis
Ce rcospo ra sc i rp icola
St reptomyces sp .
Mycobacter ium smegma t i s
St reptomyces g r i seus
CONSTANTS m . p . ° [α]Ό
188-191
187-189
186-190
—
205-206
250-252
—
—
-
—
124-126.5; 141-143; 177.5-179 (solvates)
125-126
133-135
145
-
-
217-220
-
199-204
—
173-175
+ 60
+ 88[c]
+ 85.5[el
—
+ 58[e]
+ 73[c]
—
—
—
-
+ 86[d]
+ 92[d]
+ 85[dl
-
-
-
+ 62[pl
-
—
—
-
"
R E F .
S-852
S-823
B-41
C-122
L-522
T-954
C-122
F-228
S-873
T-954
K-459
K-470
C-110
L-522
K-470
C-114
T-954
T-958
K-472
W-1092
S-820
V-1059
188
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C21H3402
^ 2 l " 3 4 ^ 3
C 2 1 H 3 4 0 4
NAME OF REACTION PRODUCT
3/3-hydroxy-5a-pregnan-20-one
3a-hydroxy-5/3-pregnan-20-one
3/3-hydroxy-5/3-pregnan-20-one
3)3, 7/3-dihydroxy-5a-pregnan-20-one
3/3, l l a -d ihyd roxy-5a -pregnan-20-one
3/3,16a-dihydroxy-5a-pregnan-20-one
3/3,16a-dihydroxy-5/3-pregnan-20-one
3/3,21-dihydroxy-5a-pregnan-20-one
3a, 21 -dihydroxy-5/3-pregnan-20-one
3/3,21-dihydroxy-5/3-pregnan-20-one
3/3,16a,20a-tr ihydroxy-17ß-me thy l -18 -no r -5a ,17q -13 -pregnene
3ß,4/3,5a- t r ihydroxy-pregnan-20-one
3/3, 5a, 6/3-trihydroxy-pregnan-20-one
3a, 6a, l l a - t r i h y d r o x y - 5 ß -pregnan-20-one
TRANSFORMATION
3 - C = 0 - 3 / 3 - O H ; Δ4-+5α-Η
3 - C = 0 - + 3 a - O H ; Δ 4 ^ 5 β - Η
3-C = 0 ^ 3 / 3 - O H ; Δ4-*5/3-Η
7/3-OH
l i a - O H
3 - C = 0 ^ 3 ß - O H
16a-OH
16a-OH; 3/3-OAC-3/3-OH
3-C = 0 - 3 / 3 - O H ; Δ4 - 5 a - H
16a-OH
3 - C = 0 - 3 / 3 - O H
3-C = 0 -3/3-OH; Δ4-+5α-Η
3 - C = 0 - 3 a - O H ; Δ 4 -5 /3 -Η
3-C=0—3/3-OH; Δ 4 -5 /3 -Η
16a, 17a -oxide -♦ 16a-OH; 13/3-CH3->17/3-CH3; 2 0 - C = O - 2 0 a - O H ; Δ13
4/3, 5/3 - oxide — 4/3,5a-diOH; 3-C = 0 - 3 / 3 - O H
5a, 6a-oxide—» 5a,6/3-diOH
l i a - O H
YIELD %
8
80
-
-
5
23
60-70
~
-
-
-
-
53
~
-
92
40
44
ORGANISM
Pénic i l l ium notatum
Streptomyces g r i seus
Al te rnar ia bataticola
Clost r id ium paraputr i f icum
Clost r id ium te r t ium
Al te rnar ia bataticola
Rhizopus a r r h i z u s
Rhizopus nigr icans
Saccharomyces ce rev i s iae
Streptomyces sp„
Streptomyces roseochromogenus
Streptomyces g r i seus
Streptomyces sp.
St reptomyces g r i seus
Streptomyces g r i seus
Al te rnar ia bataticola
Clost r idium paraputr i f icum
Clost r id ium te r t ium
Al te rna r ia batat icola
Saccharomyces ce rev i s iae
Saccharomyces ce rev i s iae
Saccharomyces ce rev i s iae
Calonectr ia decora
CONSTANTS m . p . ° [α]Ό
200
192-195
142
149-150
-
188-192
194-195
178-181
179-181
258-260
258-260
-
198-199
168-174
139-145
149-151
-
-
200-201
235-237
248-251
223-225
+ 94[c]
+ 96
+108[cl
-
+ 90
+ 78[cl
+ 70[c]
+ 62[cl
-
-
-
-
-
+ 99[cl
-
-
+ 79[c]
—
+ 61 [m]
R E F .
C-86
V-1059; W-1097
S-852
S-823
S-823
S-852
M-601; E-202
M-601
C-83; C-89
N-653; W-1092
W-1092
V-1059
W-1092
V-1059
V-1059; W-1097
S-852
S-823
S-823
S-852
C-88
C-87; C-90
C-87
S-812
189
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
C21 H34°4
C21H3405
C21 H36°4
1 C22H2402C1F
C 22 H 24°2 C 12
C22H2502C1
C22H2503F
C22H2504F3
C22H2505N
NAME O F REACTION PRODUCT
3/3,7/3,11a - t r ihydroxy- 5a -pregnan-20-one
3/3,7/3,21 - tr ihydroxy-5/3-pregnan-20-one
3ß, l l ß , 16α-tr ihydroxy-5α-pregnan-20-one
3ß, l l ß , 21- t r ihydroxy-5α-pregnan-20-one
3α, l l ß , 21- t r ihydroxy-5β-pregnan-20-one
3ß ,17a ,21 - t r i hyd roxy-5a -pregnan-20-one
3α, 17α, 21- t r ihydroxy-5ß-pregnan-20-one
3ß, 17α, 21- t r ihydroxy-5ß-pregnan-20-one
3 ß, l l ß , 17a ,21- te t rahydroxy-5a-pregnan-20-one
3a, l l ß , 17a ,21- te t rahydroxy-5ß-pregnan-20-one
3ß, 4ß , 5a, 20ß- te t rahydroxy-pregnane
17a -chlor ethinyl -6 -f luor o -1 7 ß - m e t h o x y - l , 4 , 6 -andros ta t r ien -3 -one
6-chlor o-17α-chlor ethiny 1-1 7 ß - m e t h o x y - l , 4 , 6 -andros t a t r i en -3 -one
17α-chlor e thinyl-17ß-hydr oxy -6 -methyl - 1 , 4 , 6 -andros ta t r ien -3 -one
17α -ethiny 1 -9α -fluor o -17β -hydr oxy -16α - methyl - 1 , 4 -androstadiene - 3 , 1 1 -dione
6α, 9α, 21 - t r i f luoro-17a-hy d r o x y - 2 - m e t h y l - 1 , 4 -p regnad iene -3 ,11 ,20 - t r ione
7a-cyano-17a , 21 -dihydroxy-1 ,4 -p regnad iene -3 ,11 ,20 -t r ione
TRANSFORMATION
7β-ΟΗ; 11α-ΟΗ
7β-ΟΗ
16α-OH
3 - C = 0 - * 3 ß - O H ; Δ 4 - + 5 α - Η
3 - C = 0 ^ 3 a - O H ; Δ 4 ^ 5 β - Η
3 - C = 0 - » 3 ß - O H
3 - C = 0 - 3 ß - O H ; Δ 4 - 5 α - Η
3 - C = 0 ^ 3 a - O H ; Δ 4 - 5 β - Η
3 - C = 0 - ^ 3 ß - O H ; Δ 4 - 5 β - Η
3-C=0->3ß-OH; Δ 4 ^ 5 α - Η
3 - C = 0 - > 3 a - O H ; Δ 4 ^ 5 β - Η
4ß ,5ß-ox ide-» 4ß,5a-diOH
Δ1
1
Δ
1
Δ
1
Δ
Δ 1 (2a-CH3)
1
Δ
1
YIELD %
9 .5
—
—
—
—
49
—
—
18
—
43
—
—
—
—
—
ORGANISM
Rhizopus n igr icans
Rhizopus sp.
Didymella vodakii
Streptomyces gr i seus
Al te rna r ia batat icola
Streptomyces griseus
Streptomyces au reus
Streptomyces griseus
Al t e rna r i a batat icola
Al te rna r ia bataticola
Catenabacter ium sp0
A l t e rna r i a batat icola
Saccharomyces ce rev i s i ae
Septomyxa affinis
Septomyxa affinis
Septomyxa affinis
Corynebacter ium s implex
Septomyxa affinis
Corynebacter ium s implex
CONSTANTS m.p.° [α]Ώ
268-270
205-213
257-260
—
196-197
226-230d
203-205
215-225
184-186
—
276-280
—
—
—
—
—
+103[m]
+106[e]
—
—
+ 88
+440 5[d]
+ 62
+ 48
-
—
—
—
—
—
—
—
REF.
M-601
K-433
W-1092
V-1059
S-852
V-1059
K-471
V-1059
S-852
S-852
T-973
S-852
C-87
0-694
0-694
0-694
O-701
B-43
B-75
190
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C22H2506N
C2 2H2 602Bra2F
C22H26O2CIF
^ 2 2 ^ 2 6 ^ 4
P^22"26^4^2
^ 2 2 " 2 6 ^ 5
C 2 2 H 2 6 0 5 F 2
^ 2 2 " 26^6
C22H27O2CI
C22H2702C12F
C22H2702C12I
ρ-/22"27^2·^
NAME OF REACTION PRODUCT
6a-cyano-16a ,17a , 2 1 - t r i -hy dr oxy -1 ,4 -pre gnadiene -3 ,11 ,20- t r ione
17a-bromo-9a , 11/3-dichloro-2 1 - f l u o r o - 6 a - m e t h y l - l , 4 -pre gnadiene -3 ,20 -dione
17a -chlor ethinyl -6a -fluor 0 -17ß-methoxy - 1 , 4 - a n d r o -Stadien-3-one
3,14/3-dihydroxy-l ,3,5(10), 20(22) -cardate t raenol ide
6a, 9a -difluoro -17a -hydroxy -2 -methy l -1 ,4 -p regnad iene-3 ,11 ,20- t r ione
6a, 21 -difluoro-17a -hydroxy -2 -me thy l -1 ,4 -pregnadiene -3 ,11 ,20- t r ione
17a,21-dihydroxy-16-methylene -1 ,4 -pr egna -d i e n e - 3 , l l , 2 0 - t r i o n e
17a ,21-dihydroxy-6-methyl -1,4,6 -pr egnatr iene -3 ,11 ,20- t r ione
6a ,9a -d i f l uo ro - l l j 3 , 17a ,21 -t r ihydroxy -16 -méthylène -1,4 -pre gnadiene - 3 , 2 0 -dione
3,17α, 21 -tr ihydroxy -19 -nor -1,3,5(10) -pregnatr iene -11,20-dione 21-aceta te
17a -chlor ethinyl -17/3 -methoxy-1 ,4 -andros tad ien-3-one
17a-chlorethinyl-17/3-hy dr oxy - 6a - methyl - 1 , 4 -androstadien-3 -one
9a, l l ß -d i ch lo ro -21- f luo ro -6a -methy l -1 ,4 -pregnadiene -3 ,20-dione
9a, l l ß - d i c h l o r o - 6 a - m e t h y l -21 - iodo -1 ,4 -pre gnadiene -3,20-dione
21-fluor 0 -6a -methy l -1 ,4 ,9(11)-pregnatr iene -3,20-dione
TRANSFORMATION
16a-OH
1
Δ
1
Δ
1
Δ ; enol.
Δ 1 ; 10 /3 -HC=O-10/3-H; enol.
3 / 3 - O H - 3 - C = 0 ; 5/3-ΟΗ^Δ4; Δ 1 ; 10/3-HC=O-10/3-H; enol.
Δ ' ^ α - ^ )
A1(2a-CH3)
1
Δ
1
Δ
1
Δ
A 1 ; 21-OPr—21-OH
1
Δ ; enol.
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
YIELD %
—
—
—
-
—
—
—
—
-
—
—
—
—
—
ORGANISM
Streptomyces roseochromogenus
Corynebacter ium simplex
Septomyxa affinis
Nocardia r e s t r i c t u s
Nocardia r e s t r i c t u s
Nocardia r e s t r i c t u s
Septomyxa affinis
Septomyxa affinis
Corynebacter ium simplex
Septomyxa affinis
Nocardia opaca
Mycobacter ium phlei
Corynebacter ium simplex
Septomyxa affinis
Septomyxa affinis
Corynebacter ium s implex
Corynebacter ium simplex
Corynebacter ium s implex
CONSTANTS m . p . ° [ÛÎ]D
— —
— —
— —
- -
263-265d + 78[p]
— —
— —
218-219 +103[dl
— —
- -
— —
— —
— —
— —
— —
R E F .
B-74
R-759
0-694
K-481
K-481
K-481
B-43
B-43
M-558
H-395
A-7
A-7
H-386
0-694
0-694
R-755
R-755
R-755
191
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
^-'22"27^2·'·
C 22H27O3 B r
C22H2703C1
C22H2703C12F
C22H2703C12I
C22H2703F
^22-"27^3^
C 2 2 H 2 7 0 4 F
C22H2704F3
C22H2705Br
C22H2705C1
C22H2705F
NAME OF REACTION PRODUCT
2 1 - i o d o - 6 a - m e t h y l - l , 4 , 9(11) - p r e g n a t r i e n e - 3 , 2 0 -dione
9 a - b r o m o - 1 7 a - e t h i n y l - l l ß , 17ß-dihydr oxy-16a-methyl -1,4 -andr ostadien -3 -one
9a -ch lo ro-17a-e th iny l - l l /3 , 1 7ß -dihydr oxy -16a -methyl -l , 4 - and ros t ad i en -3 -one
9a, 1 Iß -dichlor o-21 -fluor 0-17a -hydroxy -6a -methyl -1,4 -pr egnadiene -3 ,20 -dione
9a, l lß -d ich loro-17a-hydroxy-2 1 - i o d o - 6 a - m e t h y l - l , 4 -pr egnadiene -3 ,20 -dione
17a -e th iny l -9a - f luo ro - l lß , 17ß-dihydroxy-16a-methyl -1,4 -andr ostadien -3 -one
6a- f luoro-17a-hydroxy-21-methyl-1 ,4 ,9(11) -pregna-t r iene -3 ,20 -dione
17a-hydroxy-21- iodo-6a-methy l -1 ,4 ,9 (11) -p regna-t r i ene -3 ,20 -d ione
9a -f luor 0 -1 I ß , 17a -dihydr oxy-16-méthy lène-1 ,4 -p r egna-diene-3 ,20-dione
6a- f luor0-17a-hydroxy-2-me thy l -1 ,4 -p r egnadiene-3 ,11 ,20 - t r ione
6 a , 9 a , 2 1 - t r i f l u o r o - l l ß , 1 7 a -dihydroxy -2 -me thy l -1 ,4 -pregnadiene -3 ,20-dione
9a -b romo- 17a, 21 -dihydroxy -1 6 a - m e t h y l - l , 5 - p r e g n a -diene - 3 ,11 ,20 - t r ione
9a-bromo-17a ,21-d ihydroxy-16/3 - methyl - 1 , 5 -pr egna -d i e n e - 3 , l l , 2 0 - t r i o n e
16 -ch lo rome thy lene - l l ß , 17α, 21 - t r i hyd roxy - l , 4 -p regna-diene-3 ,20-dione
9 a - f l u o r o - l l ß , 1 7 a , 2 1 - t r i -hydr oxy -16 - méthylène -1 ,4 -pregnad iene-3 ,20-dione
16- f luoromethy lene- l lß , 17α, 21 - t r ihydroxy-1 ,4 -p regna -diene-3,20-dione
TRANSFORMATION
I1
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
Δ1 (2α - CH3)
Δ1 (2a - CH3)
21-OAc - 21-OH
21-OAc - 21-OH
1
Δ
1
Δ
1
Δ
YIELD %
—
—
—
—
—
—
—
—
—
—
—
48
67
ORGANISM
Corynebacter ium s implex
Corynebacter ium simplex
Corynebacter ium s implex
Corynebacter ium s implex
Corynebacter ium s implex
Corynebacter ium simplex
Mycobacterium phlei
Corynebacter ium simplex
Bacillus sphaer icus
Septomyxa affinis
Septomyxa affinis
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Corynebacter ium s implex
Bacil lus sphaer icus
Corynebacter ium s implex
CONSTANTS m.p.° [α]Ό
— —
— —
— —
— —
— —
— —
271-275 +30fe]
— —
— —
— —
— —
223-224 -34[d|
246-248 +27jd]
263-264 +25fd]
REF .
R-755
O-701
O-701
R-759
R-759
O-701
H-391
R-759; R-756
B-68
B-43
B-43
N-690; N-692
N-690; N-692
W-1084
M-558
W-1084
192
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C 2 2 H 2 7 0 5 F
C22H2705N
^ 2 2 " 2 7 ^ 6 ^
C22H2707N
^ 2 2 " 2 8 ^ 2
C22H2802C12
^ 2 2 · " 2 8 ^ 3
1 ^ 2 2 " 2 8 ^ 3 · ^ 2
NAME OF REACTION PRODUCT
6a-f luoro-17a,21-dihydroxy-2-methyl -1 ,4-pregnadiene -3 ,11 ,20 - t r ione
6j3-fluoro-17a, 21 -dihydroxy-2 - methy l -1 ,4 -pr egnadiene -3 ,11 ,20 - t r ione
9a-f luoro-17a,21-dihydroxy-16a -me thy l - l , 5-pregna -diene -3 ,11 ,20 - t r ione
9a-f luoro-17a ,21-dihydroxy-16/3-methyl - l ,5 -pregna-d iene -3 ,11 ,20- t r ione
16- f luoromethy l - l l /3 ,17a ,21-t r i hyd roxy -1 ,4 ,15 -p regna -t r i ene-3 ,20-d ione
7a - cyano - l l / 3 , 17a ,21 - t r i -hydroxy-1 ,4-pregnadiene -3,20-dione
7 ß - c y a n o - l l ß , 1 7 α , 2 1 - t r i -hydroxy-1 ,4-pregnadiene -3,20-dione
9ö-fluoro-15j3,17α, 21 - t r i -hydr oxy -15a - methyl -1 ,4 -pr egnadiene -3 ,11 ,20 - t r ione
17a, 21 - dihydr oxy -16a -n i t romethy l -1 ,4 -pr egna -d iene -3 ,11 ,20 - t r ione
6 a - m e t h y l - l , 4 , 9 ( l l ) -p regna t r i ene-3 ,20-d ione
6 / 3 - m e t h y l - l , 4 , 9 ( l l ) -pregnat r iene -3 ,20-dione
6j3-methyl-9a, l l ß - d i c h l o r o -1,4 -pr egnadiene - 3 , 2 0 -dione
17a-[2 ' - car boxy ethyl]-17/3-hydroxy -1 ,4 -andr ostadien -3-one lactone
17a-hydroxy -16-méthylène-1,4 -pr egnadiene -3 ,20 -dione
17a-hydroxy-21-methyl -1 ,4 , 9 ( l l ) - p r e g n a t r i e n e - 3 , 2 0 -dione
l l a - h y d r o x y - 1 6 a , 1 7 a , 2 1 -[ 3 , 1 , 1 - (2-pyrazol ino)]-4-pregnene-3 ,20-d ione
TRANSFORMATION
Δ1 (2α - CH3)
Δ1 (2a - CH3)
21-OAc - 21-OH
21-OAc - 21-OH
1 Δ
1
Δ
1 Δ
1
Δ
1 Δ
1 Δ
1
Δ
1 Δ
1 Δ
1
Δ
1
Δ
l l a - O H
YIELD %
-
—
—
—
68
—
—
-
—
—
—
—
—
67
ORGANISM
Septomyxa affinis
Septomyxa affinis
Fla vo bac ter ium dehydrogenans
Flavobacter ium dehydrogenans
Corynebacter ium simplex
Corynebacter ium simplex
Septomyxa affinis
Corynebacter ium simplex
Septomyxa affinis
Septomyxa affinis
Bacil lus sphaer icus
Cor ynebacter ium s implex
Corynebacter ium simplex
Corynebacter ium simplex
Ar throbac te r sp.
Bacil lus sphaer icus
Nocardia opaca
Metar rh iz ium sp.
Rhizopus n igr icans
CONSTANTS m.p.° [α]Ώ
-
—
—
—
224-225
—
—
-
—
—
134-136; 179-180
—
—
245-247
245-247
-
—
—
—
+23[d]
—
—
—
—
—
—
—
—
+392[cl
R E F .
B-43
B-43
N-690; N-692
N-690; N-692
W-1084
B-75
B-75
B-75
B-75
B-44
R-751
R-755
R-754
R-754
C-121
B-68
H-391
M-593
W-1113
193
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
^ 2 2 " 28^3-N 2
^ 2 2 ^ 2 8 ^ 4
C22H2804Br2
C22H2804FI
1 ^ 2 2 " 2 8 ^ 4 - ' : ,2
1 C22H28U5
1
NAME OF REACTION PRODUCT
l l j3 -hydroxy-16a ,17a ,21-[ 3 , 1 , 1 - (2 -pyrazolino)] -4 -pregnene-3 ,20-d ione
3 .12-d ike to -b i snor -4 , 6-choladienic acid
11/3,17a-dihydroxy-16-methylene -1 ,4 -pr egnadiene -3 ,20-dione
17a ,21-dihydroxy-16-methy lene -1 ,4 -pre gnadiene -3,20-dione
17a -hy dr oxy - 16a - me thy l -1 ,4 -p r e ^ n a d i e n e - 3 , 1 1 , 2 0 -t r ione
21-hydroxy -16a -me thy l -1 ,4 -pr egnad iene -3 ,11 ,20-tr ione
21-hydr oxy -17a -me thy l -1 ,4 -pregnadiene - 3 , 1 1 , 2 0 -t r ione
9 a , l l / 3 - d i b r o m o - 1 7 a , 2 1 -d ihydroxy-6-methy l -1 , 5-pr egnadiene -3 ,20 -dione
l l /3- f luoro-9a- iodo-16a-me thy l -1 , 5-pre gnadiene -3,20-dione
6a ,9a -d i f luoro - l l /3 ,17a-dihydroxy -2 - me thy l -1 ,4 -pr egnadiene-3,20-dione
6a ,21-d i f luoro- l l /3 ,17a-dihydroxy-2 - m e t h y l - 1 , 4 -pregnadiene-3 ,20-d ione
l l a , 1 7 a , 2 1 - t r i h y d r o x y - 1 6 -methylene -1 ,4 -pr egnadiene -3,20-dione
l l / 3 ,17a ,21- t r ihydroxy-16-methy lene -1 ,4 -pr egnadiene -3 ,20-dione
17a,21-dihydroxy-16j3-m e t h y l - 9 a , l l a - o x i d o - l , 4 -pr egnadiene -3 ,20-dione
17a, 21 -dihydr oxy -6a -methyl -1,4-pr egnad iene -3 ,11 ,20-t r ione
TRANSFORMATION
11/3-OH
7 α - Ο Η - Δ 6 ; 3 a - O H - 3 - C = 0 ; Δ4(5/3-Η); 17^-CH(CH3)-(CH2)2-COOH-17j3-CH(CH3)-COOH
1
Δ 11/3-OH
1 Δ
1 Δ
1 Δ
1
Δ ; 21-OAC-21-OH
21-OAC-21-OH
21-OAC-21-OH
Δ (2a-CH3)
Δ1(2a-CH3)
11a-OH
1 Δ
9(11) Δ —»9a, 11a-oxide; Δ 1 ; Δ4(5α-Η); 21-OAC-21-OH
1
Δ
YIELD %
6
—
—
—
—
—
—
—
—
—
—
—
—
-
ORGANISM
Cunninghamella sp.
Curvular ia lunata
St reptomyces gelat icus
Bacil lus sphaer icus
Curvular ia lunata
Bacil lus sphaer icus
Bacil lus lentus
Bacil lus lentus
Didymella lycopers ic i
F lavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Septomyxa affin is
Septomyxa affin is
Pénic i l l ium sp.
Bacil lus sphaer icus
Bacil lus sphaer icus
Corynebacter ium s implex
Baci l lus sphaer icus
Septomyxa affinis
CONSTANTS m.p.° [a]D
255-258
255-258
238-241
222-226
219-220
179-181
183-186d
—
—
—
—
—
225-226
210-211
196-198
230-232
+450[cl
- 37.5[c]
- 16[c]
—
—
+120[el
—
—
—
—
—
+ 22
+ 67[d]
-
R E F .
M-593
W-1113
H-359
B-68
B-68
M-558
R-750
R-750
V-1052; W-1096
N-691
N-691
B-43
B-43
M-558
M-558
T-981
C-138
G-300
L-512; S-833
194
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
^ 2 2 " 2 8 ^ 5
C 2 2 H 2 8 0 5 F I
^ 2 2 ^ 2 8 ^ 6
C22H2806FN
C22H28OgF2
C22.n29U2r
C 2 2 H 2 9 ° 3 F
C22H2904 F
NAME OF REACTION PRODUCT
17a, 21-dihydr oxy-6/3-methyl-1 ,4 -p regnad iene-3 ,11 ,20-tr ione
17a,21-dihydroxy-16a-methyl -1 ,4 -pr egnadiene -3 ,11 ,20- t r ione
17a,21-dihydroxy-16/3-me thy l -1 ,4 -pr egnadiene -3 ,11 ,20- t r ione
17a,21-dihydroxy-16a-methy l -1 ,5 -pr egnadiene -3 ,11 ,20- t r ione
1 la, 21 - dihydr oxy -16/3 -methy l -1 ,5 -pregnadiene -3 ,11 ,20- t r ione
l l /3 ,17a ,21- t r ihydroxy-6-methyl - 1 , 4 , 6 -pr egnatr iene -3,20-dione
l l j3 ,17a ,21- t r ihydroxy-16-me thy l -1 ,4 ,15 -p r egna-t r iene-3 ,20-dione
l l j3 - f luoro-6ß ,17a ,21- t r i -hydr oxy- 9a - iodo -16a -methyl -1 ,4 -pregnadiene -3,20-dione
6/3,17a, 21 - t r ihydroxy-16a-methy 1-1,4 -pr egnadiene -3 ,11 ,20- t r ione
15/3,17a,21-tr ihydroxy-15a-methy 1-1,4 -pr egnadiene -3 ,11 ,20- t r ione
6a-cyano-9a-f luoro-l l / 3 , 1 6 a , 1 7 a , 2 1 - t e t r a -hydroxy-4-pregnene-3 ,20-dione
6a, 9a-difluoro-ll/3,16a,17a,21 -te t rahydroxy-12a-methyl -1,4 -pregnadiene - 3 , 2 0 -dione
21 - f l uo ro -17a -me thy l - l , 4 -pre gnadiene -3 ,20 -dione
6a-f luoro-17a-hydroxy-16a-methy 1 -1 ,4 -pre gnadiene -3,20-dione
9a-f luoro- l l /3-hydroxy-6a-methyl -1 ,4 -pregnadiene -3,20-dione
6a-f luoro- l l /3 ,17a-dihydroxy-2 - methy l -1 ,4 -pregnadiene -3,20-dione
TRANSFORMATION
Δ1
1
Δ
Δ 1 ; Δ (5α-Η)
Δ 1 ; Δ4(5α-Η); 21-OAC-21-OH
21-OAC-21-OH
21-OAC-21-OH
1
Δ
1
Δ
6/3-OH
6β-ΟΗ
1
Δ
16a-OH
1
Δ
1
Δ
1
Δ
1
Δ
Δ1(2α-ΟΗ3)
YIELD %
—
—
46
—
—
—
57
—
—
60
—
—
ORGANISM
Septomyxa affinis
Bacil lus lentus
Corynebacter ium s implex
Corynebacter ium simplex
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Septomyxa affinis
Corynebacter ium simplex
Chaetomium funicolum
Chaetomium funicolum
Septomyxa affinis
Streptomyces roseochromogenus
Nocardia aurant ia
Septomyxa affinis
Calonectr ia decora
Septomyxa affinis
Septomyxa affinis
CONSTANTS m.p.° [α]Ό
— —
199-202 -
200-205 +198[d|
— —
— —
221-222 —
250-251 + 18[c]
— —
— —
- -
— —
— —
R E F .
S-833
R-750
K-451
K-451
N-690; N-692
N-690; N-692
H-395
W-1084
N-691
N-690; N-692
B-44
B-74
F-260
S-901
W-1090a
S-927; S-923
B-43
195
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
^ 2 2 " 29^4 '
C22H2905Br
C22H2905C1
C2 2H2 905F
NAME OF REACTION PRODUCT
6a-f luoro-17a ,21-dihydroxy-1 6 a - m e t h y l - l , 4 -p regna-diene-3 ,20-dione
9a- f luoro- l l /3 ,17a-d ihydroxy-6a - methyl -1 ,4 -pr egnadiene -3,20-dione
9a - f luor 0 -15a - hy dr oxy - 6a -methyl-4 -pr egnene -3 ,11 ,20 - t r i one
9 a - b r o m o - l l / 3 , 1 7 a , 2 1 - t r i -hydr oxy -16a -me thy l -1 ,4 -pr egnadiene -3 ,20 -dione
9 a - b r o m o - l l / 3 , 1 7 a , 2 1 - t r i -hy dr o x y - 1 6 a - m e t h y l - 1 , 5 -pre gnadiene -3 ,20 -dione
9 a - b r o m o - l l / 3 , 1 7 a , 2 1 - t r i -hydroxy -16/3-methyl - 1 , 5 -pr egnadiene-3,20-dione
9 a - c h l o r o - l l / 3 , 1 7 a , 2 1 - t r i -hydr oxy -16a -me thy l -1 ,4 -pr egnadiene-3 ,20-dione
16 -chlor o m e t h y l e n e - l l ß , 1 7 a , 21- t r ihydroxy-4-pregnene-3,20-dione
9 a - c h l o r o - l l / 3 , 1 7 a , 2 1 - t r i -hydroxy-16a -me thy l -1 ,5 -pregnadiene -3 ,20 -dione
9 a - c h l o r o - l l / 3 , 1 7 a , 2 1 - t r i -hy dr oxy-160-methy l -1 , 5-pregnadiene -3 ,20 -dione
6a - f l uo ro - l l j 3 , 17a ,21 - t r i -hy dr oxy - 2 - methy 1 - 1 , 4 -pregnadiene-3 ,20-d ione
6 a - f l u o r o - l l ß , 1 7 a , 2 1 - t r i -hydr oxy-16α-methy l -1 ,4 -pregnadiene-3 ,20-d ione
6 j3- f luoro- l l /3 ,17a ,21- t r i -hydroxy - 2 - methyl - 1 , 4 -pregnadiene -3 ,20 -dione
9 a - f l u o r o - l l / 3 , 1 7 a , 2 1 - t r i -hydr oxy - 6a - methyl - 1 , 4 -p r egnadiene-3 ,20-dione
9 a - f l u o r o - l l / 3 , 1 7 a , 2 1 - t r i -hy dr oxy -16a - methy 1 - 1 , 4 -pregnadiene-3 ,20-d ione (dexamethasone)
9a - f l uo ro - l l j 3 , 17a ,21 - t r i -h y d r o x y - 1 6 a - m e t h y l - l , 5 -pr egnadiene-3 ,20-dione
TRANSFORMATION
Δ1
1
Δ
15a-OH
1
Δ
21-OAC-21-OH
21-OAC-21-OH
1
Δ
llj3-OH
21-OAC-21-OH
21-OAC-21-OH
A1(2a-CH3)
1
Δ
A1(2a-CH3)
1
Δ
1
Δ
21-OH
21 - O A c - 2 1 -OH
YIELD %
67
—
—
—
—
—
—
58(cr.)
—
—
—
75-85
—
32
-
ORGANISM
Actinoplanes mi s sou r i ens i s
Septomyxa affinis
Pénic i l l ium ur t icae
Corynebacter ium s implex
Flavobacter ium dehydrogenans
F lavobacter ium dehydrogenans
Corynebacter ium s implex
Curvular ia lunata
F lavobacter ium dehydrogenans
F lavobacter ium dehydrogenans
Septomyxa affinis
Corynebacter ium simplex
Septomyxa affinis
Bacillus sphaer icus
Septomyxa affinis
Bacil lus lentus
Colletotr ichum lindemuthianum
Flavobacter ium dehydrogenans
CONSTANTS m . p . ° [oi]D
177-179 —
292-303 -
— —
— —
— —
— —
— —
228 + 40[d]
— —
— —
— —
— —
— —
243-250 + 93 [a]
221-223 —
R E F .
M-536
L-513
A-31
R-752
N-690; N-692
N-690; N-692
R-752
W-1084
N-690; N-692
N-690; N-692
B-43
U-1042
B-43
G-300
S-921
R-750
M-598
N-690; N-692
196
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C22H2905F
C 2 2 H 2 9 ^ 6 F
C22H2906N
C22H2907N
^ 2 2 · " 3 0 ^ 2
1 ^-/22"30^'3
NAME OF REACTION PRODUCT
9a - f luo ro - l l / 3 ,17a ,21 - t r i -hydroxy-16/3-methyl-1, 5-pregnadiene-3 ,20-dione
16- f luoromethyl - l l /3 ,17a ,21-t r ihydroxy-4 ,15-p regna-diene - 3 , 20-dione
6 a - f l u o r o - l l a , 1 7 a , 2 1 - t r i -hydroxy -16 - méthylène -4 -pregnene-3 ,20-dione
16-f luoromethylene-l l /3 , 17a, 21 - t r ihydroxy -4 -pregnene -3,20-dione
6a-fluor o-9a-methy 1-11/3,16α, 17α, 21 - t e t r a -hydroxy-1,4-pregnadiene -3,20-dione
6a-f luoro- l l /3 ,14a , 17a, 2 1 -te t r ahy dr oxy -16a - methy 1-1,4 -pregnadiene - 3 , 20 -dione
9a - f l uo ro - l l / 3 , 16a ,17a ,21 -t e t r ahyd roxy -2 -me thy l - l , 4-pregnadiene-3 ,20-dione
9 a - f l u o ro - l l / 3 , 16a ,17a ,21 -te t rahydroxy-6a-methyl -1,4 -pr egnadiene - 3,20 -dione
6 a - c y a n o - 1 6 a , 1 7 a , 2 1 - t r i -hydroxy-4-pregnene-3 ,11 ,20- t r ione
l l /3 ,17a ,21- t r ihydroxy-16a-nitr omethy 1-1,4 -pre gna -diene-3 ,20-dione
17a-al ly l -17j3-hydroxy- l ,4-androstadien-3 -one
17a-isopropenyl-17/3-hydr oxy -1 ,4 -andr ostadien -3-one
16a-methyl -1 ,4-pregnadiene -3,20-dione
17a-methy 1-1,4-pregnadiene-3,20-dione
20-methoxy- l ,4 ,17(20) -pregna t r i en-3 -one
3 -keto -bisnop-1,4 -chola-dienic acid
21-hydr oxy-17a-methy 1-1,4-pregnadiene -3 ,20 -dione
TRANSFORMATION
21-OAc -21-OH
11/3-OH; 21-OAc - 2 1 -OH
l l a - O H
11/3-OH
1
Δ
1
Δ
16a-OH
16a-OH
16a-OH
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
3 / 3 - O H - 3 - C = 0 ; Δ5 — Δ 4 ; Δ 1 ; 17/3-[2T-isooctyll— 17j3-[2' -propionic acid]
1
Δ ; 21-OAc—21-OH
YIELD %
—
19
—
48
80-85
—
—
—
—
-
—
-
55
-
62(cr.)
ORGANISM
Flavobacter ium dehydrogenans
Curvular ia lunata
Rhizopus n igr icans
Curvular ia lunata
Nocardia aurant ia
Corynebacter ium simplex
Streptomyces argenteolus
Streptomyces roseochromogenus
Streptomyces roseochromogenus
Bacil lus sphaer icus
Didymella lycopers ic i
Didymella lycopers ic i
Bacil lus lentus
Septomyxa affinis
Septomyxa affinis
Nocardia sp.
Septomyxa affinis
CONSTANTS m.p.° [α]Ώ
— —
210-211 + 70[d]
— —
239-241 + 85[dl
— —
— —
— —
— —
- —
— —
116-117 —
160 + 38[c]
- -
154.5-156.5 -
R E F .
N-690; Ί N-692
W-1084
A-7
W-1084
F-260
U-1042
H-380
F-257
B-74
R-751
W-1109
W-1109
R-750
S-901
F-251
W - l l l l
S-901
197
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
^22 " 3 0 ^ 3
1 C 22™ 3QPA
C22H30O4ClF
C 22H30O4 C l 2
NAME O F REACTION PRODUCT
l l ß , 2 1 - d i h y d r o x y - 2 - m e t h y l -1,4,17(20) - p r e g n a t r i e n - 3 -one
lljS, 21 - dihy dr oxy - 6a - methyl -1,4,17(20) -pr egnat r ien-3 -one
16/3-methyl-16a, 17a-oxido-4-pregnene-3 ,20-d ione
1 7 ß - h y d r o x y - l ß , l l ß - o x i d o -5 ,9-cyc loandros tan-3-one 17-propionate
17a-[2 ' -carboxyethyl]-7a, 17β -dihy dr oxy - 4 -androsten - ' 3-one spirolactone
1 7 a - [ 2 ' - c a r boxy ethyl]-9a, 17ß-dihydroxy-4-andros ten-3 -one spirolactone
11/3,17a-dihydroxy-16a-m e t h y l - l , 4 - p r e g n a d i e n e -3,20-dione
l l ß ,21 -d ihyd roxy-16a -methyl -1 ,4 -pr egnadiene -3,20-dione
17a, 21-dihy dr oxy-16a-methyl -1 ,4 -pr e gnadiene -3,20-dione
11a ,17a-dihydroxy-16-methylene-4-pregnene -3,20-dione
l l ß , 17a-dihydroxy-16-méthylène-4-pregnene -3,20-dione
17a ,21-dihydroxy-16-méthylène -4 -pregnene -3,20-dione
15a-hydr oxy-6a-me thy 1-4-pr egnene -3 ,11 ,20 - t r ione
16a - hydr oxy - 6a - methyl - 4 -pregnene -3 ,11,20 - t r ione
21-hydroxy-12a-methy l -4 -p regnene -3 ,11 , 20- t r ione
9 a - c h l o r o - l l ß - f l u o r o - 1 7 a , 2 1 -d ihydroxy-2a-methy l -5 -pregnene-3 ,20-d ione
9 a , l l ß - d i c h l o r o - 1 7 a , 2 1 -dihy dr oxy - 6 - methyl - 5 -p regnene-3 ,20-d ione
TRANSFORMATION
A ^ a - C H g )
1
Δ
3 ß - O H - 3 - C = 0 ; Δ 5 - Δ 4
A ' - l l ß - O A c -Ι β , Ι Ι β - o x i d e
7a-OH
9a-OH
1
Δ
1
Δ
1
Δ
l l a - O H
l l ß - O H
3 ß - O A c - 3 - C = 0 ; 21-OAC-21-OH; Δ 5 - Δ 4
15a-OH
16a-OH
21-OH
21-OAC-21-OH
21-OAC-21-OH
YIELD
% 1 -
-
42
—
—
—
—
—
—
—
—
-
—
—
49(cr.)
—
ORGANISM
Septomyxa affinis
Septomyxa affinis
F lavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Gelas inospora t e t r a s p o r a
Nocardia sp.
Bacil lus lentus
Bacil lus lentus
Bacil lus lentus
F u s a r i u m sp.
Curvular ia lunata
F lavobacter ium dehydrogenans
Pénic i l l ium ur t icae
St reptomyces roseochromogenus
Cercospore l l a herpotr ichoides
Kabatiel la phoradendr i
F lavobacter ium dehydrogenans
F lavobac te r ium dehydrogenans
CONSTANTS m . p . ° [of]D
-
-
164
268-270
228-230
212.5-213
192-193.5
209-212
208-210
216-217
207
-
-
-
149-151
—
—
-
-
"
+ 44
+ 76[c]
—
—
+ 46[d]
- 8 [ c ]
+ 42[c]
+ 47.5[c]
-
-
-
+207.5[c
—
R E F .
M-573; H-394
M-573; S-928
S-837
R-777
T-1035
D-173
R-750
R-750
R-750
B-68
B-68
T-981 ; M-558
A-31
S-834
L-490
L-498
N-691
N-691
198
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
^ 2 2 " 3 0 ^ 5
NAME OF REACTION PRODUCT
la - hy dr oxy - 3 ,12 - diketo -bisnor-4-cholenic acid
l l a , 1 7 a , 2 1 - t r i h y d r o x y - 6 £ -methyl -1 ,4 -pr egnadiene -3,20-dione
l l a , 1 7 a , 2 1 - t r i h y d r o x y - 1 6 a -methyl -1 ,4 -pregnadiene -3,20-dione
l l a ,17a ,21- t r ihydroxy-16 /3 -methy 1 -1 ,4 -pr e gnadiene -3,20-dione
l l /3 ,17a ,21- t r ihydroxy-2-methyl -1 ,4 -pr egnadiene -3,20-dione
11/3,17a, 21- t r ihydroxy-6a-metl iyl-1,4 -pr egnadiene -3,20-dione
l l /3 ,17a,21- t r ihydroxy-6/3-methyl -1 ,4 -pregnadiene -3,20-dione
l l /3 ,17a ,21- t r ihydroxy-16a-methy 1 -1 ,4 -pr egnadiene -3,20-dione
11/3,17a, 21-trihydroxy-16/3-methy 1 -1 ,4 -pr e gnadiene -3,20-dione
TRANSFORMATION
7-C=0->7a-OH; Δ4(5/3-Η) ; 17ß-CH(CH3)-(CH2)2-COOH^17/3-CH(CH3)-COOH
3a-OH->3-C=0; 1 2 a - O H - 1 2 - C = 0 ; Δ4(5/3-Η); 17/3-CH(CH3)-(CH2)2-COOH-17/3-CH(CH3)-COOH
1
Δ
l l a - O H
11a-OH
1
Δ
A(2a-CE3)
A1(2a-CH3); 21 -OAc-21-OH
1
Δ 1
Δ
1
Δ
1
Δ
11/3-OH 1
Δ ; 21-OAC-21-OH
11/3-OH
YIELD %
1
—
—
-
-
-
-
-
2
46(cr.)
—
—
-
-
ORGANISM
Streptomyces gelaticus
Streptomyces gelaticus
Septomyxa affinis
Beauveria sp.
Glomerel la cingulata
Pesta lot ia foedans
Phoma sp .
Beauveria sp.
Glomerel la sp.
Phoma sp.
Corynebacter ium simplex
Septomyxa affinis
Nocardia coral l ina
Bacil lus sphaer icus
Septomyxa affinis
Septomyxa affinis
Bacillus lentus
Bacil lus sphaer icus
Phoma sp.
Bacil lus sphaer icus
Phoma sp.
CONSTANTS m.p.° [α]Ό
278-280
280-282d
—
—
236-238
—
-
-
-
270-272
245-247
—
219-220
-
-
+ 77fe]
—
—
+ 2 4 i d l
—
-
-
-
-
+ 83[d]
—
—
-
-
REF.
H-363
H-354
S-833
1-421
C-109
Ü-702
1-422
1-421
C-109
1-422
1-421
H-394; M-573
H-399
G-300
L-512; S-833; W-1072; M-647; M-573; K-456
L-512; S-833
R-750
H-392
1-422
T-986
1-422
199
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
^ ■ ^ " β θ ^
I ^ 2 2 " 3 0 ^ 6
C2 2Hs l03Br
C 2 2 H 3 1 0 3 F
C 2 2 H 3 1 0 4 F
C 2 2 H 3 1 ° 5 F
NAME OF REACTION PRODUCT
l l ß , 1 7 a , 2 1 - t r i h y d r o x y - 1 6 a -m e t h y l - l , 5 - p r e g n a d i e n e -3,20-dione
l l ß , 1 7 a , 2 1 - t r i h y d r o x y - 1 6 ß -methy 1-1 ,5-pregnadiene-3,20-dione
l l ß , 1 7 a , 2 1 - t r i h y d r o x y - 1 6 -methy l -4 ,15-pregnad iene-3,20-dione
17a,21-dihydroxy-16ß-methyl-1 - 5α-pr egnene -3 ,11 ,20 - t r i one
17a ,21-dihydroxy-16a-methy 1 -1 - 5ß-pregnene -3 ,11 ,20 - t r ione
l l a , 1 7 a , 2 1 - t r i h y d r o x y - 1 6 -methylene -4 -pregnene -3,20-dione
l l ß , 1 7 a , 2 1 - t r i h y d r o x y - 1 6 -methylene -4 -pr egnene -3 ,20-dione
17a,21-dihydroxy-16ß-methyl-9a , l l a - o x i d o - 4 -pregnene-3 ,20-d ione
11/3,15/3,17a, 21-tetrahydroxy-15a-methyl - 1 , 4 - p r egna-diene-3 ,20-dione
11/3,16a, 17a, 21 - tetrahydroxy-6a -me thy l -1 ,4 -p regnad iene -3,20-dione
1 7 a - b r o m o - l l ß - h y d r o x y - 6 a -methyl -4-pr egnene -3 ,20 -dione
6a-fluoro-11/3-hydroxy-17a-me thy l -4 -p regnene -3 ,20 -dione
6 ß - f l u o r o - l l a , 17a-dihydroxy-21-methy l -4 -pregnene-3,20-dione
6/3-f luoro-l lß, 17a-dihydroxy-21-methy l -4 -pregnene-3,20-dione
6 a - f l u o r o - l l a , 1 7 a , 2 1 - t r i -hydroxy-16a-methyl -4-pregnene-3 ,20-d ione
6 a - f l u o r o - l l ß , 1 7 a , 2 1 - t r i -hy dr oxy -16a - methy 1 - 4-p regnene-3 ,20-d ione
TRANSFORMATION
21-OAc^21-OH
21-OAC-21-OH
l l ß - O H
1 Δ
1
Δ ; 21-OAc^21-OH
Δ 4 ^ 5 β - Η
l l a - O H
l l ß - O H
9(11) Δ - 9 a , 1 l a - o x i d e ; Δ4(5α-Η); 21-OAC-21-OH
Δ1
16a-OH
l l ß - O H
l l ß - O H
l l a - O H
l l ß - O H
l l a - O H
l l a - O H ; 21-OAC-21-OH
l l ß - O H
YIELD
% 1
27
-
4
—
-
—
—
—
—
—
—
-
70-75
ORGANISM
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Curvular ia lunata
Cor ynebacter ium s implex
Corynebacter ium s implex
Streptomyces sp .
F u s a r i u m sp.
Curvular ia lunata
Corynebacter ium s implex
Septomyxa affin is
St reptomyces roseochromogenus
Curvular ia lunata
Curvular ia lunata
Rhizopus n igr icans
Curvular ia lunata
Epicoccum oryzae
Aspergi l lus ochraceus
Aspergi l lus ochraceus
Curvular ia lunata
CONSTANTS m.p.° [a]p|
— —
245-247 + 53[c]
- -
206-212 +116[d]
199-201 + 42[d]
224-225 + 69[d]
— —
— —
— —
— —
— —
— —
216.5-218.5 —
REF.
N-690; 1 N-692
N-690; N-692
W-1084
K-451
K-451
G-314
M-558
M-558; T-981
C-138
B-44
F-257
R-756; R-759
R-759
H-391
H-391
H-391
W-1098
W-1098
U-1042
200
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C 2 2 H 3 1 0 5 F
C22H3106F
^ 2 2 ^ 3 2 ^ 2
C22H3203
NAME OF REACTION PRODUCT
6a - f luo ro - l l / 3 ,17a ,21 - t r i -hydr oxy - 21 - me thyl -4 -pregnene-3 ,20-dione
6a - f luo ro -14a ,17a ,21 - t r i -hydroxy -16a - me thyl - 4 -pregnene-3 ,20-dione
21- f luo ro - l l / 3 ,16a ,17a - t r i -hydroxy-6a-methyl -4-pregnene-3 ,20-dione
6 a - f l u o r o - l l a , 1 4 a , 1 7 a , 2 1 -te t rahydroxy-16a-methyl -4-pregnene-3 ,20-dione
6a- f luoro- l l /3 ,14a , 1 7 a , 2 1 -te t r ahydr oxy -16a - methyl -4-pregnene-3 ,20-dione
6a- f luoro- l l /3 ,16a , 17a, 21 -te t r ahydr oxy -9a - methyl -4-pregnene-3 ,20-d ione
9 a - f l u o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 -te t r ahydr oxy -2 ξ -methyl -4-pregnene-3 ,20-dione
9a-fluor o-11/3,16a, 17a, 21 -te t rahydroxy-12a-methyl -4-pregnene-3 ,20-d ione
17/3-hydroxy-4-androsten-3-one 17-propionate
3 - k e t o - 2 0 - M i s o " - b i s n o r - 4 -cholen-22-al
15a -hydroxy -3 -keto - bisnor -4-cholen-22-a l
3 -keto-bisnor -4-cholenic acid
7/3-hydroxy-7a-methyl-4-pregnene-3 ,20-d ione
11a-hydroxy-16a-methyl -4-pregnene-3 ,20-d ione
11a -hydroxy - 17a-methyl -4-pregnene-3 ,20-dione
Hj3-hydroxy-6j3-methyl-4-pregnene-3 ,20-d ione
s t e reochemis t ry a t 20- of sta
TRANSFORMATION
11/3-OH; 21-OAc^21-OH
14a-OH
16a-OH
11a-OH
11/3-OH
16a-OH
16a-OH
16a-OH
3 / 3 - O H - 3 - C = 0 ;
Δ 5 - Δ 4
20-HC=O-> 20-" i so"-HC=O*
15a-OH
3/3-OH-*3-C = 0 ; Δ 5 - + Δ 4 ; 17j3-(2' -isooctyl)-» 17j3-(2' -propionic acid)
3/3-OH-*3-C = 0 ; Δ 5 - Δ 4 ; 20 /3-OH-20-C = O
l l a - O H
l la -OH
11/3-OH
rung mater iaLnot cjef]
YIELD %
—
0.5-2
—
1
15-25
—
—
"
—
9
-
35
-
—
ned
ORGANISM
Curvular ia lunata
Curvular ia lunata
Streptomyces roseochromogenus
Cunninghamella elegans
Cunninghamella elegans
Streptomyces roseochromogenus
Streptomyces argenteolus
Streptomyces roseochromogenus
Acetobacter pas teur ianum
Gliocladium catenulatum
Fusa r ium solani
Nocardia sp.
F lavobacter ium dehydrogenans
Rhizopus n igr icans
Aspergi l lus ochraceus
Cunninghamella blakesleeana
Curvular ia lunata
CONSTANTS m.p.° [α]Ό
— —
247-251 +124[dl
— —
— —
— —
— —
— —
"
121 + 87[e]
— —
— —
154-157 +121[dl
161-163 +149[cl
— —
— —
R E F .
H-390
U-1042
L-510
U-1042
U-1042
F-260
H-380
F-260
K-457
W-1068
M-599
W - l l l l
R-776
S-804; L-515; L-517; C-141
V-1048; S-835
L-520
R-754; R-757; R-773
TABLE I
T r a n s f o r m a t i o n s by Product
201
EMPIRICAL FORMULA
C22H32O4
^ 2 2 " 3 2 ^ « î
NAME OF REACTION PRODUCT
1 l a - hydr oxy - 3 -keto - bisnor -4-cholenic acid
11a, 17a-dihydroxy-16a-methyl-4 -pregnene -3 ,20 -dione
11a ,17a-d ihydroxy-21-me thy l -4 -p regnene -3 ,20 -dione
11/3,16a-dihydroxy-6a-methyl-4 -pregnene -3 ,20 -dione
11/3,16a-dihydroxy-12a-m ethyl -4 -pre gnene -3 ,20 -dione
11/3,17a-dihydroxy-21-methyl-4 -pregnene - 3 , 2 0 -dione
17a, 21-dihydroxy-16a-me thy l -4 -p regnene -3 ,20 -dione
17a, 21 - dihydroxy -16/3 -me thy l -4 -p regnene -3 ,20 -dione
2ß ,17a ,21- t r ihydroxy-16a-me thy l -4 -p regnene -3 ,20 -dione
l l a , 1 7 a , 2 1 - t r i h y d r o x y - 1 6 a -me thy l -4 -p regnene -3 ,20 -dione
l l a , 17a ,21 - t r i hyd roxy-16 /3 -me thy l -4 -p regnene -3 ,20 -dione
11/3,16a, 17a- t r ihydroxy-6a-methyl-4 -pregnene - 3 , 2 0 -dione
l l / 3 ,17a ,21- t r ihydroxy-2a -methyl-4 -pregnene - 3 , 2 0 -dione
l l ß , 1 7 a , 2 1 - t r i h y d r o x y - 1 6 a -methyl-4 -pregnene - 3 , 2 0 -dione
l l /3 ,17a ,21- t r ihydroxy-16ß-me thy l -4 -p regnene -3 ,20 -dione
TRANSFORMATION YIELD
l l a - O H
11a-OH; 17a-OH
l l a - O H
16a-OH
16a-OH
l l ß - O H
3/3-OH—3-C=0; Δ5 - Δ 4 ; 21-OAC-21-OH
3 ß - O A c - 3 - C = 0 ; Δ 5 - > Δ 4 ; 21-OAc-»21-OH
2β-ΟΗ
l l a - O H
l l a - O H
l l a - O H ; 21-OAc^21-OH
16a-OH
21-OAC-21-OH
l l ß - O H
11/3-OH
55
ORGANISM
Sporotr ichum sulfurescens
Dactylium dendroides
Rhizopus n igr icans
St reptomyces roseochromogenus
St reptomyces roseochromogenus
Curvular ia lunata
F lavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Gnomonia f ragar iae
Beauver ia sp .
Glomere l la cingulata
Phoma sp.
Beauver ia sp.
Glomere l la cingulata
Phoma sp.
Beauveria sp.
Glomere l la cingulata
St reptomyces roseochromogenus
Nocardia cora l l ina
Curvular ia lunata
Phoma sp .
Phoma sp.
CONSTANTS m.p.° [a]D
219-220
196-198
fl30[d]
- 61[c
R E F .
220-222 +110[d]
M-582
M-571
H-391
S-834
F-257
H-391
C-109; 1-421; 1-422
C-109; 1-421; 1-422
L-496
1-421
C-109
1-422
1-421
C-109
1-422
1-421
C-109
L-511
H-399
C-96
1-422
1-422
202
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
^22"32^5
^22"32^6
C22H33ON
^22"34^2
^22^34^3
C22 H34°4
C 22H34O5
NAME OF REACTION PRODUCT
15α, 17α, 21- t r ihydr oxy-16a-methy l -4 -p regnene-3 ,20-dione
l l /3 ,14a ,17a ,21- te t rahydroxy-16a-methy l -4-pregnene-3,20-dione
4-conenin-3-one
22 -hy dr oxy - bisnor -4 -cholen -3-one
2 2 - hy dr oxy - 2 0/3-bisnor-4-cholen-3-one
Γ7/3, 19-dihydroxy-17a-propyl -4-andros ten-3-one
1 l a , 22 -dihydr oxy - bisnor - 4 -cholen-3-one
15α, 22 -dihydr oxy -bisnor - 4 -cholen-3-one
6/3, l i a , 22 - t r ihydr oxy -bisnor -4-cholen-3-one
3a ,7a -d ihydroxy-12-ke to -bisnor - 5j3-choIanic acid
l l a , 1 7 a , 2 1 - t r i h y d r o x y - 1 6 a -methyl-5a -pregnane -3 ,20 -dione
l l a ,17a ,21- t r ihydroxy-16 /3 -methyl- 5a -pregnane - 3 , 2 0 -dione
11/3,17a, 21 - t r ihydr oxy -16a -me thy l -5a -p regnane -3 ,20 -dione
11/3,17a, 21-tr ihydr oxy-16ß-methyl-5a -pregnane - 3 , 2 0 -dione
TRANSFORMATION
15a-OH
11/3-OH; 14a-OH
3 /3 -N(CH 3 ) 2 -3 -C=0 ; Δ 5 ^ Δ 4
20-HC=O-^ 20a-CH2OH
2 0 - H - C = O ^ 20/3-CH2OH
19-OH
l l a - O H
l l a - O H ; 22-C=0->22-OH
15a-OH; 2 2 - C = 0 ^ 2 2 - O H
6/3-OH
6ß-OH; l l a - O H ; 22-C = 0-»22-OH
12a-OH->12a-C = 0 ; 17/3-CH(CH3)-CH2-CH 2 -COOH-17ß-CH(CH3)-COOH
l l a - O H
l l a - O H
11/3-OH
11/3-OH
YIELD %
—
—
35
-
20
8
-
-
15
—
4
30
2-12
-
—
-
—
ORGANISM
Curvular ia lunata
Curvular ia lunata
Gloeosporium cyclaminis
Hypomyces haematococcus
Gliocladium catenulatum
Pénici l l ium l i lacinum
Hypochnus sasaki i
Sporotr ichum sulfurescens
Rhizopus n igr icans
Rhizopus n igr icans
Cunninghamella blakesleeana
Rhizopus a r r h i z u s
Rhizopus n igr icans
Streptomyces gelat icus
Beauveria sp.
Glomerel la cingulata
Phoma sp.
Beauveria sp .
Glomerel la sp.
Phoma sp.
Phoma sp .
Phoma sp.
CONSTANTS m.p.° [a]D
—
—
108-110
-
133-146
143-145
-
-
130-133
-
222-228
238-240
232-238
:
-
—
-
—
—
—
+160[d]
-
-
+ 98[cl
-
-
+ 78[cl
-
-
+ 22[c]
-
:
-
—
R E F .
C-96
C-96
D-148
D-148
W-1068
W-1068; E-202
S-869
M-582
M-578; M-601
E-202
M-578
M-578
M-578; M-601
H-359
1-421
C-109
1-422
1-421
C-109
1-422
1-422
1-422
203
TABLE I I I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C23H2403C1F
C 2 3 H 2 4 0 3 C 12
C23H2603C1F
1 C23H2603C12
C23H2703C1
1 ^23^27^3-k
C 2 3 H 2 7 0 4 I
C23H2709C1S
|C23H28Ü3
C 2 3 H 2 8 0 4 C 12
|C23H2805
IC23H2806
NAME OF REACTION PRODUCT
17a-chlore th inyl -6-f luoro-17 /3-hydroxy- l ,4 ,6 -andro-s t a t r i en -3 -one aceta te
6-ch loro-17a-chlore th inyl -17 j3-hydroxy- l ,4 ,6 -andro-s t a t r i en -3 -one aceta te
17a - chlor ethiny 1 - 6a - fluor o -17/3 - hy dr oxy -1 ,4 - andr o -Stadien-3-one aceta te
6a - chlor o- 17a -chlor ethiny 1-17/3-hydr oxy-1 ,4 -andr o-s tadien-3-one ace ta te
17a-chlorethinyl-17ß-hydr oxy -1 ,4 -andr ostadien -3-one aceta te
17a - ethiny 1 -16a - ethyl - 9a -f luoro-17/3-hydroxy- l ,4-androstadiene -3 ,11 -dione
17a-hydroxy-21-iodo-1,4,9 ( 11) -pre gnatr iene -3,20-dione aceta te
1 2 a - c h l o r o - l l j 3 , 1 6 a , 1 7 a , 2 1 -t e t r ahyd roxy-1 ,4 -p regna -d iene-3 ,20-dione 16 ,17-cyclosulfate 21-acetate
17a - ethiny 1 -16a - ethyl -17/3-hydroxy-9/3, l l ß - o x i d o - 1 , 4 -andros tadien-3 -one
17ß-hydroxy-16a-methyl-17a-(l f -propinyl)-9/3,11/3-oxido-1,4 -andr os tadien-3 -one
17/3-hydroxy-16a -methyl - Ha-il' -pr opiny 1)-1 ,4-andr o-stadien - 3 , 1 1 - dione
9a, l l j3-dichloro-17a-hydroxy-1,4 -pr egnadiene -3 ,20 -dione aceta te
14/3-hydroxy-3,19-dioxo-4,20(22)-cardadienolide
21-hydroxy-16a ,17a-oxido-1,4-pr egnad iene-3 ,20-dione aceta te
17a, 21-dihydr oxy - 1 , 4 -pr egnad iene-3 ,11 ,20- t r ione 21 -acetate
1 7 a , 2 1 - d i h y d r o x y - l , 4 -p regnad iene -3 ,11 ,20 - t r ione 21-aceta te 4-Ci*
TRANSFORMATION
Δ^
1
Δ
1
A
1
Δ
l
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1 9 - O H - 1 9 - C = 0
3/3-OH-3-C = 0 ; 5 /3 -ΟΗ-Δ 4
1
Δ
1
Δ
1
Δ
YIELD
% 1
1̂ —
—
—
—
—
—
—
—
—
—
8
-
—
11
6
ORGANISM
Corynebacter ium s implex
Corynebacter ium simplex
Corynebacter ium simplex
Corynebacter ium simplex
Corynebacter ium simplex
Corynebacter ium simplex
Corynebacter ium simplex
Bac te r ium cyclooxydans
Corynebacter ium simplex
Corynebacter ium simplex
Corynebacter ium s implex
Corynebacter ium s implex
Pénic i l l ium thomii
Chaetomium globosum
No cardia r e s t r ictus
Bac te r ium havaniensis
Corynebacter ium s implex
Bacil lus sphaer icus
CONSTANTS m.p.° [α]Ό
"
— —
— —
— —
— —
— —
— —
— —
— —
— —
230-235 +129[c]
222-224 —
- -
— —
230-233d —
- -
R E F .
0-694 1
0-694
0-694
0-694
0-694
O-701
R-756
F-262
O-701
O-701
O-701
G-307
S-892
S-891
K-481
F-233
N-665
C-120
204
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
C23H2902C12I
C 23 H29O3F
^ 2 3 H 2 A B r
C23H 2 90 5 F
C23H2906F
^ 2 3 " 3 ( Γ Λ
^23 " 3 0 ^ 4
C 2 3 H 3 0 ° 4 C 12
C2 3 H3 0 O5
NAME OF REACTION PRODUCT
9 a , l l ß - d i c h l o r o - 2 1 - i o d o -6 a , 1 7 a - d i m e t h y l - l , 4 -pregnadiene-3 ,20-dione
1 la - ethiny 1 -16a - ethyl - 9a -f luoro-l lß ,17/3-di hydroxy -l , 4 - andros t ad ien -3 -one
9 a - b r o m o - 1 6 a - e t h y l - 1 7 a , 2 1 -dihydroxy-1, 5-pregnadiene -3 ,11 ,20- t r ione
16a-e thy l -9a- f luoro-17a ,21-dihydroxy-1,5-pregnadiene -3 ,11 ,20- t r ione
9 a - f l u o r o - l l ß , 1 7 a , 21 - t r i -hydroxy -1 ,4 -pr egnadiene -3,20-dione 21-acetate
6 , 1 7 a - d i m e t h y l - l , 4 , 6 -pregna t r iene-3 ,20-d ione
14/3 -hydroxy -3 -keto -4,20(22)-cardadienolide
21 -hydroxy -1 ,4 -pre gnadiene -3,20-dione aceta te
9a, l l ß - d i c h l o r o - 6 , 1 6 a -dimethyl-17a, 21-dihydroxy-1,5 -pr egnadiene - 3 , 2 0 -dione
9a, l lß -d ich lo ro-6 ,16 /3-dimethyl-17a, 21-dihydroxy-1,5 -pr egnadiene - 3 , 2 0 -dione
14/3,19-dihydroxy-3-keto-4,20(22)-cardadienolide
14/3-hydroxy-3,16-diketo-5ß-20(22)-cardenolide (tentative)
11/3,17a, 21 -tr ihydroxy -6a-methy l -16-méthy lène-1 ,4 -pregnadiene-3 ,20-dione
17a ,21-dihydroxy-6a ,16a-dimethyl -1 ,4 -pregnadiene -3 ,11 ,20- t r ione
16a - ethyl -17a, 21 - dihy dr oxy -1, 5 -p regnad iene-3 ,11 ,20-t r ione
11/3,17a, 21 -tr ihydroxy -6a, 16-d i m e t h y l - l , 4 , 1 5 - p r e g n a -t r i ene -3 ,20-d ione
TRANSFORMATION
Δ1
1 Δ
21-OAc^21-OH
21-OAC-21-OH
1 Δ
1 Δ
5/3-Η-Δ4
(via 5ß-OH)
3/3-OH-3-C = 0 ; 5 ß - H - Δ 4 ( v i a 5ß-OH)
1 Δ
21-OAC-21-OH
21-OAc->21-OH
1 9 - C = 0 - 1 9 - O H
3 ß - O H - 3 - C = O j 16ß -OH-16-C = 0
1 Δ
1
Δ
21-OAc^21-OH
1 Δ
YIELD %
—
—
—
—
79
—
<1
67(cr.)
55
—
—
ORGANISM
Corynebacter ium simplex
Corynebacter ium simplex
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Bacter ium havaniensis
Bac te r ium mycoides
Septomyxa affinis
Absidia orchid is
Mucor pa ras i t i cus
Absidia orchid is
Mucor pa ras i t i cus
Corynebacter ium simplex
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Pénici l l ium thomii
Gibberel la fujikuroi
Corynebacter ium s implex
Bacillus sphaer icus
Flavobacter ium dehydrogenans
Corynebacter ium s implex
CONSTANTS \m.y.° [e]p
— —
— —
— —
— —
121-121.5 + 13[c]
— —
229-236 —
202-204 +143[cl +152[el
247-251 —
— —
236-237 + 5[d]
"
— —
246-248 + 10[d]
R E F .
R-759
O-701
N-692
N-690; N-692
F-233
F-240
S-901
N-682
N-682
N-679
N-678
H-389; N-671
N-691
N-691
S-892
K-434
B-69
A-24; A-25
N-690; N-692
B-69
205
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
r^23"30^5
C23H30O5NF
IC23H30Ue
| ^ 2 3 " 3 0 ^ 7
C23H3105Br
C 2 3 H 3 1 ° 5 F
1 C23H3202
1 ^23 " 3 2 ^ 3
NAME OF REACTION PRODUCT
l l /3 ,16a ,21- t r ihydroxy-1 ,4 ,17(20) -c i s -p regna t r i en-3-one 21-aceta te
21-hydroxy-16a ,17a-oxido-4-pregnene-3 ,20-d ione aceta te
21 - (N-acetylamino) -9a -f luor o -l l / 3 , 1 7 a - d i h y d r o x y - l , 4 -pregnadiene-3 ,20-d ione
Π β , 17α, 21 - t r i hyd roxy-1 ,4 -pregnadiene-3 ,20-d ione 21-aceta te
l l /3 ,21-d ihydroxy-16a ,17a-ox ido-4 -p regnene-3 ,20-dione 21-aceta te
14a ,21-d ihydroxy-16a ,17a-ox ido-4 -p regnene-3 ,20-dione 21-aceta te
11/3,14a,21-tr ihydroxy-16a, 17a-oxido-4-pregnene -3,20-dione
9a -b romo-16a-e thy l -l l ß , 1 7 a , 2 1 - t r i h y d r o x y - l , 5 -pregnadiene-3 ,20-d ione
9 a - f l u o r o - l l / 3 , 1 7 a , 2 1 - t r i -hydroxy-6a, 16a-dimethyl-1,4 -pregnadiene -3 ,20 ~ dione
16a - ethyl - 9a -fluoro-11/3,17a, 21 - t r ihydroxy - 1 , 5 -pregna-diene-3 ,20-dione
17a-e thy l -1 ,4 -pregnad iene-3,20-dione
6α, 17α-d imethy l -1 ,4 -pregna-diene-3 ,20-dione
1,4-pregnadiene -3 ,20-dione 20-cycloethylene ketal
TRANSFORMATION
^
3/3-OH-3-C = 0 ; Δ 5 - Δ 4
1 Δ
21-OH^21-AcNH
1 Δ
11/3-OH
14a-OH
l l ß - O H ; 14a-OH
21-OAC-21-OH
1 Δ
21-OAC-21-OH
1 Δ
1 Δ
1 Δ
YIELD %
—
—
—
13
—
—
—
—
—
25
27
-
-
—
—
ORGANISM
Septomyxa affinis
F lavobacter ium sp.
Corynebacter ium simplex
Streptomyces roseochromogenus
Bacter ium cyclooxydans
Corynebacter ium s implex
Curvular ia lunata
Curvular ia lunata
Curvular ia lunata
Flavobacter ium dehydrogenans
Mycobacter ium smegmat i s
Flavobacter ium dehydrogenans
Septomyxa affinis
Septomyxa affinis
Bacter ium cyclooxydans
Bacil lus sphaer icus
Corynebac ter ium hoagii
Cylindrocarpon radic icola
St reptomyces lavendulae
CONSTANTS m.p.° MD[
—
—
252-255 (ethanol solvate)
—
237-239d
—
—
—
—
—
150-151
118-119
-
-
—
—
—
—
+107[ml
—
-
—
—
—
—
—
-
+ 14[c]
-
-
—
-
R E F .
M-529
P-742
S-911
S-911
K-480
N-665
A-3 ; A-5
A-3 ; A-5
A-3 ; A-5
N-690; N-692
A-24; A-25
N-690; N-692
S-901
S-901
F-251
F-251
F-251
F-251
F-251
206
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C^HggOg
^ 2 3 " 3 2^4
^ 2 3 Η 3 2 ϋ 5
NAME OF REACTION PRODUCT
1 ,4-pregnadiene -3 ,20-dione 20-cycloethylene ketal
3/3,14/3-dihydroxy-5/3-16, 20 (22) -cardadienolide (tentative)
3/3-hydroxy-14a, 15a-oxido-5/3-20(22) -cardenolide
14/3-hydroxy-3-keto-5/3,17a-20(22)-cardenolide
14/3-hydroxy-3-keto-5/3-20(22)-cardenolide
5 / 3 - 1 - p r e g n e n e - 3 , 1 1 , 2 0 -tr ione 20-cycloethylene ketal
21-hydroxy-4-pregnene-3 ,20-dione acetate
7/3,14/3-dihydroxy-3 -keto-5/3-20(22)-cardenolide
12/3,14/3-dihydroxy-3-keto-5/3-20(22) -cardenolide
TRANSFORMATION
3/3-OH-*3-C = 0 ; Δ5—>Δ4· Δ1
Δ 1 6
3j3-OAc^3/3-OH
3/3-OH-*3-C = 0
3 a - O H - 3 - C = 0
3/3-OH-3-C = 0
1
Δ
3/3-OH->3-C = 0 ; Δ 5 - Δ 4
7/3-OH
3/3-OH-*3-C = 0
7/3-OH; 3/3-OH-3-C = 0
7/3-OH; 3/3-OAc-3-C = 0
12/3-OH
YIELD %
-
1
93
:
4
-
—
10
-
-
2
-
2
-
2
-
-
44
-
5
-
1
13
-
ORGANISM
Septomyxa affinis
Tr ichothecium roseum
Rhizopus shanghaiensis
Calonectr ia decora
Mucor pa ras i t i cus
Nigrospora sphaer ica
Rhizopus a r rh i zus
Calonectr ia decora
Mucor pa ras i t i cus
Nigrospora sphaer ica
Rhizopus a r r h i z u s
Absidia sp.
Aspergi l lus oryzae
Cunninghamella sp.
Mucor pa ra s i t i cus
Mucor sp.
Psi locybe mexicana
Rhizopus sp.
Tr ichothecium roseum
Septomyxa affinis
Flavobacter ium sp0
Psi locybe mexicana
Rhizopus a r r h i z u s
Rhizopus a r rh i zus
Psi locybe mexicana
Rhizopus a r rh i zus
Rhizopus a r rh i zus
Calonectr ia decora
CONSTANTS m.p.° [α]Ό
-
—
-
—
219-223
-
—
198-204
-
-
-
-
197-205
-
205-207
-
-
204-206
—
266-273
-
259-269
261-275
—
-
—
-
—
-
-
—
-
-
-
-
-
-
-
-
-
-
—
—
+ 56[cl
-
:
—
"
REF.
F-251
T-1013
M-576
N-681
N-681
N-681
N-681
N-681
N-681
N-681
N-681
N-682
J-432
N-682
N-678
N-682
W-1075
N-682
J-432
F-253; F-249; F-251
P-742
W-1075
N-678
N-678
W-1075
N-678
N-678
N-677
207
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
*-'23"32^'5
NAME OF REACTION PRODUCT
12)3,14/3-dihydroxy-3-keto-5/3-20(22)-cardenolide
14/3,16/3-dihydroxy-3-keto-5)3-20(22) -cardenolide
1 6 a - e t h y l - l l a , 1 7 a , 2 1 - t r i -hydroxy-1 ,4-pregnadiene -3,20-dione
1 6 / 3 - e t h y l - l l a , 17a ,21 - t r i -hydroxy-1 ,4-pregnadiene -3,20-dione
16j3-e thyl - l l /3 ,17a ,21- t r i -hydroxy-1 ,4-pregnadiene -3,20-dione
l l /3 ,17a ,21- t r ihydroxy-6α, 16α -dimethyl - 1 , 4 -pregnadiene -3 ,20 -dione
1 6 a - e t h y l - l l / 3 , 1 7 a , 2 1 - t r i -hydroxy-1 ,5 -p r egnadiene -3,20-dione
l l ß , 1 7 a , 2 1 - t r i h y d r o x y -6α, 16 -d ime thy l -4 ,15 -pr egnadiene-3,20-dione
11 β, 17α -dihydr oxy -1 - 5a -p regnene-3 ,20-d ione 17-aceta te
TRANSFORMATION
12j3-OH
3 ß - O H - 3 - C = 0
12/3-OH; 3 a - O H - 3 - C = 0
12/3-OH; 3j3-OH - 3 - C = 0
12/3-OH; 3/3-OAc >3-C=0
3/3-OH-*3-C = 0
3/3-OAc->3-C=0
3 ß - O A c - 3 - C = 0 ; 16j3-OAc-16j3-OH
l l a - O H ; 21 -OAc-21 -OH
l l a - O H
11/3-OH
1
Δ
21-OAC-21-OH
11/3-OH
11^-OH
YIELD %
5
50
-
13
10
-
10
10
-
8
-
—
—
—
-
—
—
—
—
ORGANISM
F u s a r i u m lini
Gibberel la saubinett i
Calonect r ia decora
Calonectr ia decora
Nigrospora sphaer ica
Calonectr ia decora
Nigrospora sphaer ica
Calonectr ia decora
Calonectr ia decora
F u s a r i u m sp.
Gibber ella fujikuroi
Nigrospora sphaer ica
Calonectr ia decora
Nigrospora sphaer ica
Calonect r ia decora
Nigrospora sphaer ica
Pes ta lo t ia foedans
Beauver ia sp.
Glo me r e l i a cingulata
Phoma sp.
Phoma sp.
Nocardia a s t é ro ïdes
Flavobacter ium dehydrogenans
Curvular ia lunata
Curvular ia lunata
CONSTANTS m.p.° [ a ] p |
247-252 (hydrate)
251-254
-
243-248
242-253
254-256
-
201-209
199-202; 215-220
-
195-198
-
—
221-222
-
—
—
—
238-240
+ 41[m]
+ 32 [lm: lc]l
-
—
—
-
-
-
-
—
+ 21[d]
-
—
—
—
+ 51[d]
R E F .
G-320; T-978
0-699
N-677
N-681
N-681
N-677
N-677
N-677
N-677
K-434
K-434
N-677
N-677
N-677
N-677
N-677
O-703
1-421
C-109
1-422
1-422
A-24; A-25
N-690; N-692
B-69
R-773
208
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
C23 H32 0 5
C23H3205NF
C23 H32°6
C23H3206NF
^ 2 3 " 34^2
^23"34^3
C23 H34 04
C23 H34°5
NAME OF REACTION PRODUCT
l l /3 ,17a ,21- t r ihydroxy-6a-methy 1 -16 - méthylène -4 -pregnene-3 ,20-d ione
17a,21-dihydroxy-4-pregnene-3,20-dione 21-acetate
21-[N-acetylamino]-9ö-f luoro-11/3,17û-dihydroxy-4-pregnene-3 ,20-d ione
3/3, 5/3,14/3-trihydroxy-19-oxo-20(22) -cardenolide (strophanthidin)
21- |N-acetylaminoj-9a-f l u o r o - 2 ß , l l ß , 1 7 a - t r i -hydroxy-4-pregnene-3 ,20-dione (tentative)
16 ,16-d imethyl -4-pregnene-3,20-dione
l la-hydroxy-6a,16û!-d imethy l -4 -p regnene-3 ,20-dione
l l /3-hydroxy-6a ,16a-d imethy l -4 -p regnene-3 ,20-dione
l l /3-hydroxy-6a ,17a-d imethy l -4 -pregnene-3 , 20-dione
3a,14/3-dihydroxy-5/3-20(22)-cardenolide
3j3,14/3-dihydroxy-5/3-20(22)-cardenolide (digitoxigenin)
6ß-hydroxy-4-pregnene-3 ,20-dione 20-cycloethylene ketal
1 la -hydroxy-4-pregnene-3 , 20-dione 20-cycloethylene ketal
l/3,3/3,14/3-trihydroxy-5/3,17a-20(22)-cardenolide (tentative)
TRANSFORMATION
11/3-OH; 21-OAc—21-OH
3/3-OH^3-C = 0 ; Δ 5 - Δ 4
3/3-OAc-*3-C=0; Δ 5 —Δ 4
21-NH2->21-AcNH
21-OH—21-AcNH
3/3-D-glucoside-^ 3/3-OH
3ß-D-glucoside tetraacetate—3/3-OH
2/3-OH
3/3-OH-3-C = 0 ; Δ 5 ->Δ 4
Πα-ΟΗ
11/3-OH
11/3-OH
3 - C = 0 ^ 3 Ö - O H
3 - C = 0 - 3 ß - O H
6ß-OH
l l a - O H
lß-OH
YIELD %
—
—
3-11
-
51
57
53
—
—
12-15
4
-
—
ORGANISM
Curvular ia lunata
Flavobacter ium sp .
Corynebacter ium simplex
Streptomyces roseochromogenus
Streptomyces roseochromogenus
Fusa r ium lini
Fusa r ium lini
St reptomyces roseochromogenus
Flavobacter ium dehydrogenans
Rhizopus n igr icans
Cunning hamella blakesleeana
Curvular ia lunata
Absidia orchidis
Fusa r ium lini
Gibberel la saubinetti
Mucor pa ras i t i cus
Mucor pa ras i t i cus
Psi locybe semperv iva
Gliocladium catenulatum
Sporotr ichum epigaeum
Absidia orchidis
CONSTANTS m.p.° [α]Ό
218
-
213-215
263-264
135-140; 198-201
133-135
168-169
—
269-282
280-284
-
"
+ 50[d]
—
-
+132[ml
-
+ 88[d] +104[cl
"
"
-
-
-
:
R E F .
B-69
P-742
C-128; N-665
S-911
S-911
T-978
T-978
S-911
S-837
S-923
S-923
R-759
N-682
T-978; G-320
0-699
N-678; N-682 N-678
W-1075
F-251
F-251
N-681
209
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C-23 H 3 4 0 5
NAME O F REACTION PRODUCT
3/3, 5/3,14/3-trihydroxy-17a-20(22)-cardenolide
I ß , 3/3,14/3- t r ihydroxy- 5/3-20(22)-cardenolide
3a, 7/3,14/3 - tr ihydroxy -5/3-20(22)-cardenolide
3a, 12/3,14/3 - tr ihydroxy -5/3-20(22)-cardenolide
3a, 14/3,16/3-trihydroxy-5/3-20(22)-cardenolide
3/3,5/3,14/3-trihydroxy-20(22)-cardenolide
3/3,7/3,14/3-trihydroxy-5/3-20 (22)-cardenolide
TRANSFORMATION
5/3-OH
1/3-OH
3 - C = 0 - 3 a - O H ; 7/3-OH
3-C = 0 - 3 a - O H ; 12/3-OH
3-C=0->3a-OH
5/3-OH
7/3-OH
YIELD %
3
17
-
-
-
-
4
1
-
-
37-40
-
24
-
22(cr.)
-
—
4
! 25
l l ( c r . )
ORGANISM
Absidia orchid is
Mucor pa ra s i t i cus
Absidia orchid is
Absidia sp.
Mucor sp.
Rhizopus n igr icans
Rhizopus sp.
Rhizopus a r r h i z u s
Fusa r ium lini
Gibberel ia saubinett i
Fusa r ium lini
Absidia orchidis
Mucor pa ras i t i cus
Rhizopus a r r h i z u s
Absidia orchidis
Absidia sp .
Aspergi l lus oryzae
Cunninghamella sp .
Mucor sp.
Ps i locybe mexicana
Rhizopus a r r h i z u s
Rhizopus a r r h i z u s
CONSTANTS m . p . ° [ a ] D
232-241d
276-282d
-
-
-
-
255-259
249-262
-
-
245-248
-
266-275
-
275-280
-
-
263-266
267-272
275-280
+ 35[m]
+ 3[m]
-
-
-
-
+ 48[ml
+ 27[m]
-
-
+ 25[cj + 28.5[ml
-
+ 37[m]
-
+ 39[m]
-
—
+ 39[m]
+ 34.5
+ 39[m]
R E F .
N-681
N-681
N-679; N-680; 1-426; N-683
N-682
N-682
N-683
N-682
N-678
G-320; T-978
0-699
T-977
N-679; N-680; N-683; 1-426
1-423; N-678; N - 6 8 3 ; N-682
N-678; N-682
N-680; N-679; 1-426; N-683; N-681
N-682
J-432
N-682
N-682; N-683
W-1075
N-678; 1-425
J-432
210
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C 23 H 34 0 5
NAME OF REACTION PRODUCT
3/3, 7/3,14/3-trihydroxy-5/3-20(22)-cardenolide
3/3,11a, 14/3-trihydroxy-5/3-20(22)-cardenolide
(sarmentogenin)
3/3,12/3,14/3-trihydroxy-5/3-20(22)-cardenolide (digoxigenin)
3/3,14/3,16/3-trihydroxy-5/3-20(22)-cardenolide (gitoxigenin)
3/3,14/3,X-trihydroxy-5/3-20(22)-cardenolide
17/3-methyl-18-nor-17a-5,13-pregnadiene-3/3,16α, 20α, 21 -t e t ro l 21-acetate
TRANSFORMATION
7/3-OH
l l a - O H
12/3-OH
12/3-OH; 3/3-OAc-3/3-OH
12/3-OH; 3-C = 0 - 3 / 3 - O H
16/3-OH
16/3-OAc-16ß-OH
3/3-OAc-3/3-OH; 16/3-OAc-16/3-OH
X-OH
20-C=O-»20a-OH; 13/3-CH3-16a,17a-oxide—17/3-CH3-18-nor -16a -OH; Δ13
YIELD %
l l ( c r . )
-
8
-
4.5
35
-
43
—
-
2
—
25
-
-
-
—
-
9(cr.)
40
ORGANISM
Rhizopus dele mar
Rhizopus sp.
St reptomyces aureofaciens
Tr ichothecium r o s e u m
Trichothecium ro seum
Trichothecium roseum
Calonectr ia decora
Fusa r ium lini
Gibberel la fujikuroi
Gibberel la saubinett i
Helicostylum pi r i forme
Nigrospora sphaer ica
Psi locybe mexicana
Psi locybe semperviva
F u s a r i u m lini
Psi locybe semperv iva
Cunninghamella blakesleeana
Helicostylum pi r i forme
Gibberel la saubinett i
Calonectr ia decora
Fusa r ium lini
Nigrospora sphaer ica
Rhizopus a r r h i z u s
Saccharomyces ce rev i s iae
CONSTANTS m.p.° [a]D
266-274d
-
268-275
-
—
207-209
-
206-209
-
197-208
-
-
210-213
-
—
-
—
-
268-276
205-210
-
-
+ 37[mj
-
—
+ 22.5[ml
-
-
-
-
-
-
-
-
—
-
+ 18[m] •
R E F .
N-682
N-682; N-683
T-1013
T-1013
J-432
T-1013
N-677
T-978; G-320; W-1074
N-651
0-699
N-651
N-677
W-1075
W-1075
T-978; G-320
W-1075
N-651
N-651
0 -699
N-677
T-977
N-677
J-432
C-90
211
TABLE I
T r a n s f o r m a t i o n s by Produc t
EMPIRICAL FORMULA
C23H3405
C^H^Og
1 C23H3604
1 ^23 "36^5
CMH2904C12F
NAME OF REACTION PRODUCT
l l j3 ,17a ,21- t r ihydroxy-6a , 16Ö -dimethyl -4 -pregnene -3 ,20-dione
1/3,3/3, 7/3, 14/3 - t e t r any droxy-5/3-20(22) -cardenol ide
3/3, 5/3, 7/3, 14/3-tetr any droxy-20(22)-cardenolide
3/3,12/3,14/3,16/3-tetr ahydroxy-5/3-20(22)-cardenolide (diginatigenin)
3/3,5/3,14/3,19/3-tetrahydroxy-20(22)-cardenolide
3a ,17a ,21- t r ihydroxy-5 /3-p r e g n a n e - l l , 2 0 - d i o n e 2 1 -aceta te
3a,21-dihydroxy-5/3-pregnan-20-one 21-aceta te
16/3-ethyl- l lö , 17α, 21 - t r i -hydroxy-5a -p regnane -3 ,20 -dione
16/3-e thyl - l l /3 ,17a ,21- t r i -hydroxy-5a -p regnane -3 ,20 -dione
9a, 11/3-dichloro-21-fluor o-17a-hydroxy-6a-methyl -1,4 -pr egnadiene -3 ,20-d ione aceta te
9a, l l /3-d ichloro-17a-hydroxy-21 - i odo -6a -me thy l -1 ,4 -pr egnadiene -3 ,20 -dione ace ta te
TRANSFORMATION
11/3-OH; 21-OAC-21-OH
1/3-OH; 7/3-OH
5j3-OH; 7/3-OH
12/3-OH
12β-ΟΗ; 16/3-OAc-16/3-OH
1 9 - C = 0 ^ 1 9 - O H
3 - C = 0 — 3 α - Ο Η ; Δ 4 - 5 β - Η
3 - C = 0 - 3 a - O H ; Δ4 -5/3-H
l l a - O H
11/3-OH
1 Δ
1 Δ
YIELD %
—
6-10
-
-
-
4-7
-
-
-
6
2
-
53
57
-
—
-
—
ORGANISM
Curvular ia lunata
Absidia orchid is
Absidia sp.
Mucor sp.
Rhizopus sp.
Absidia orchid is
Absidia sp .
Mucor sp.
Rhizopus sp.
Fusa r ium lini
Fusa r ium sp.
Gibber el la saubinett i
Gibberel la saubinett i
Ps i locybe semperviva
Clos t r id ium paraput r i f icum
Clos t r id ium t e r t i u m
Clos t r id ium paraput r i f icum
Clos t r id ium t e r t i um
Beauveria sp.
Glomere l la sp.
Phoma sp .
Phoma sp.
Corynebac te r ium s implex
Corynebac te r ium s implex
CONSTANTS m . p . ° [a]D
—
244-254d
-
-
-
249-250
-
-
-
155-156
154-156
153-156
-
216
176-178
-
—
-
—
—
+ 19[m| + 22.5[m]
-
-
-
+ 49[ml
-
-
-
—
+ 34[ml
-
-
+ 73 [a]
+100[c|
-
—
-
—
—
R E F .
S-805
N-679; N-680; 1-426; N-682
N-682
N-682
N-682
N-679; 1-426; N-682
N-682
N-682
N-682
T-977
K-434
0-699 !
0-699
W-1075
S-823
S-823
S-823
S-823
1-421
C-109
1-422
1-422
R-759
R-759
212
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C24H30O4
C^HaoOgBrF
^ 2 4 ^ 3 0 ^ 6
C^HaPeClF
^ 2 4 ^ 3 0 ^ 6 1*2
^■24"30^7
C 2 4 H 3 1 0 6 F
C24H3107F
C24H3204
1 ^ 2 4 " 32^5
NAME OF REACTION PRODUCT
17a-hydroxy-16-méthylène 1,4 -pr egnadiene -3 ,20 -dione acetate
9 a - b r o m o - l l ß - f l u o r o - 1 6 a , 1 7 a , 2 1 - t r i h y d r o x y - l , 5 -pr egnadiene-3,20-dione 16,17-acetonide
17a, 21 -dihydroxy -16a -methyl-1,4 -pregnadiene - 3 , 1 1 , 2 0 -tr ione 21-acetate
17a, 21 -dihydroxy -16/3-methyl -1 ,4 -pregnadiene 3 ,11 ,20- t r ione 21-acetate
6 a - c h l o r o - 1 2 a - f l u o r o - l l ß , 16a, 17a, 21 - te t r any droxy-1,4 -pregnadiene - 3 , 2 0 -dione 16,17-acetonide
2 , 9 a - d i f l u o r o - l l ß , 16α, 17α, 21 - te t r ahydr oxy - 1 , 4 -pr egnadiene-3,20-dione
16,17-acetonide
3, l l ß , 17a, 21- te t r ahydr oxy-19-nor - l , 3,5(10) -pregna-t r ien-20-one 1 1 , 2 1 -diacetate
9 a - f l u o r o - l l ß , 1 6 a , 1 7 a , 2 1 -t e t r ahydroxy-1 ,4 -p regna -diene-3 ,20-dione 16 ,17-acetonide
9 a - f l u o r o - 2 , l l ß , 1 6 a , 1 7 a , 2 1 -pen tahydroxy-1 ,4-pregna-diene - 3 , 20-dione 16 ,17 -acetonide
9a-f luoro-6ß, l l ß , 16α, 17α, 21-pen tahydroxy-1 ,4-pregna-diene - 3 , 20-dione 16 ,17-acetonide
9a-f luoro-6ß, 16α, 17α, 21 -t e t rahydroxy-4-pregnene-3 ,11 ,20- t r ione 16 ,17 -acetonide
3,12 -diketo - 4 , 6 - choladienic acid
12/3,14/3 -dihydroxy -3 -ke to-5ß-20,22-bufadienolide
TRANSFORMATION
Δ1
2 1 - O A c - 2 1 ~ O H
Δ1*4 (5/3-H); 3 a - O H - > 3 - C = 0
Δ 1 ' 4 (5ß-H); 3a -OH-*3-C = 0
1
Δ
A ^ a - F )
Δ ; enolo
Δ1
2-OH
1 Δ
6ß-OH; 11/3-OH—11-C=0
7 - C = 0 - Δ6
3 a - O H - 3 - C = 0 ; 7 α - Ο Η - Δ 6 ; 12a -OH-*12-C=0 ; 5/3-H— Δ4
12ß-OH
YIELD %
22
—
—
18
6
1
ORGANISM
Baci l lus sphaer icus
Flavobacter ium dehydrogenans
Nocardia blackwelli i
Nocardia blackwelli i
Nocardia aurant ia
Nocardia coral l ina
Corynebacter ium simplex
Nocardia coral l ina
Streptomyces g r i seus
Nocardia coral l ina
Phycomyces sp„
Corynebacter ium sp.
Streptomyces gelat icus
Streptomyces rubescens Fusa r ium lini
CONSTANTS m.p.° [α]Ό
222-223
—
—
277-282
243-24505
205-208
228-237
-90[d]
"
—
—
"
+72[p]
+94[m)
—
+l[m]
R E F .
S-837
N-691
S-902
S-905
F-261
H-401
H-386
H-399
F-235; F-236
H-400
H-400
T-975
H-359
H-365
T-979
213
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
^ 2 4 " 3 2 ^ 5
C 2 4 H 3 2 U 6
1 ^24 "32^7
L 2 3 n 3 2 U 7 . r 2
C 2 4 H 3 3 0 6 F
C 2 4 H 3 3 0 7 F
C 2 4 H 3 4 0 4
C 2 4 H 3 4 0 5
C24H3 30 6F
NAME OF REACTION PRODUCT
2 1-hydroxy-16/3- methyl -16a, 17a-oxido-4-pregnene -3,20-dione aceta te
l l /3 ,17a ,21- t r ihydroxy-16a-me thy 1-1 ,4-pregnadiene-3,20-dione 21-aceta te
l l /3 ,17a ,21- t r ihydroxy-16/3-methoxy - 1 , 4 - p r egnadiene-3,20-dione 21-aceta te
6a, 9a-difluor 0-2/3,11/3,16a, 17a, 21 -pentahydroxy-4-pregnene-3 ,20-d ione 16 ,17-acetonide
6a - fluor 0-2/3,16a, 17a, 21 -t e t r ahydroxy-4-p regnene-3,20-dione 16,17-acetonide
6 a - f l u o r o - l l a , 1 6 a , 1 7 a , 2 1 -t e t r ahydroxy-4-p regnene-3,20-dione 16,17-acetonide
9a- f luoro-2 j3 , l l j3 ,16a ,17a ,21-pentahydroxy-4-pregnene-3,20-dione 16,17-acetonide
9a-f luoro-6ß, 11/3,16α, 17α, 2 1 -pentahydroxy-4-pregnene-3,20-dione 16,17-acetonide
12a-hydroxy-3-keto - 1 , 4 -choladienic acid
12a-hydroxy-3-keto - 4 , 6 -choladienic acid
3/3,12/3,14/3-trihydroxy-5/3-20,22-bufadienolide
3 ,7 ,12- t r ike to-5 /3-cholan ic acid
7a -hydroxy-3 ,12-d ike to -4 -cholenic acid
6 a - f l u o r o - l l ß , 16α, 17α, 2 1 -te t r ahydr oxy-4-pr egnene -3 ,
| 20-dione 16,17-acetonide
TRANSFORMATION
3 / 3 - O H - 3 - C = 0 ; Δ 5 - Δ 4
11/3-OH
1 Δ
2/3-OH
2/3-OH
l l a - O H
2/3-OH
6/3-OH
3 a - O H - 3 - C = 0 ; 7a-OH-*H; Δ 1 ; Δ4(5β-Η)
3 a - O H - 3 - C = 0 ; 7α-ΟΗ->Δ6; Δ4(5/3-Η)
12/3-OH
3 a - O H - 3 - C = 0 ; 7a-OH->7-C = 0 ; 1 2 a - O H - 1 2 - C = 0
7-C = 0 - 7 a - O H ; Δ4(5/3-Η)
3 a - O H - 3 - C = 0 ; 12a -OH—12-C=0 ; Δ4(5/3-Η)
11/3-OH
YIELD
% 1 —
—
—
14
24
24
—
15
—
3
—
50(cr.)
65-99
-
15
2
1
—
ORGANISM
Flavobacter ium sp .
Curvular ia lunata
Cor yne bac ter ium s implex
St reptomyces g r i seus
Gnomonia f ragar iae
Col le totr ichum phomoides
Tr ichothecium r o s e u m
Streptomyces g r i seus
Phycomyces sp.
Corynebac ter ium s implex
Corynebacter ium s implex
Corynebac te r ium sp.
S t reptomyces rubescens
F u s a r i u m lini
Alcal igenes faecal is
Esche r i ch ia coli
Corynebac te r ium sp„
St rep tomyces gelat icus
S t rep tomyces rubescens
Cunninghamella b a i n i e n
CONSTANTS m . p . ° [o?]D|
—
—
—
240-242
264-266
260-261
240.5-243.5
—
249-252
-
240-246
236-237
-
246-249d
224-226d
248-252d
—
—
—
—
- 53[c]
+102[cl
+ 13[m]
+ 72[m]
—
-
- 16[m]
—
-
-
—
—
R E F .
P-742
S-904
R-760
F-235; F-236
L-496
D-159
D-159
F-235; F-236
H-400
H-358; H-367
H-367
T-974
H-362
T-979
S-799; S-800; H-393
S-799
T-975
H-363
H-365
R-771 ,
214
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
C 2 4 H3 4 0 7
^24 " 3 6 ^ 3
C2 4 H3 6 0 4
C 2 4 H3 6 0 5
^ 2 4 ^ 3 8 ^ 4
^ 2 4 " 3 8 ^ 5
C2 4 H4 0 O4
C 2 5 H 3 0 O 5 S
NAME OF REACTION PRODUCT
2/3,11/3,16α, 17α, 21-penta-hydroxy-4-pregnene-3 ,20-dione 16,17-acetonide
3-keto-4-cholenic acid
12a-hydroxy-3-ke to-4-cholenic acid
3a-hydroxy-7,12-diketo-5/3-cholanic acid
7a-hydroxy-3 ,12-d ike to-5ß-cholanic acid
la, 12a -dihydroxy -3 -keto -4 -cholenic acid
3a-hydroxy-6-keto-5/3-cholanic acid
3a-hydroxy-7-keto-5/3-cholanic acid
3a-hydroxy-12-ke to-5ß-cholanic acid
3a, 7a-dihydroxy -12 -keto-5/3-cholanic acid
3a, 12a-dihydroxy-7-keto-5/3-cholanic acid
7a, 12a-dihydroxy-3-keto-5/3-cholanic acid
3a, 7a-dihydroxy-5/3-cholanic acid
21-hydroxy-16a-mercap to-1,4,9(11) -p regna t r i ene -3,20-dione 16,21-diaceta te
unidentified gram-pos i t ive co
TRANSFORMATION
2/3-OH
3/3-OH^3-C = 0 ; Δ 5 - Δ 4
3 a - O H - 3 - C = 0 ; 7 a - O H ^ H ; Δ4(5/3-Η)
7 a - O H - 7 - C = 0 ; 1 2 a - O H - ^ 1 2 - C = 0
7-C=0-*7a-OH
3 a - 0 H - 3 - C = 0 ; 1 2 a - O H - 1 2 - C = 0
3a -OH->3-C=0; Δ4(5/3-Η)
3 - C = 0 - 3 a - 0 H
7a-OH->7-C = 0
3 - C = 0 - 3 a - 0 H
12a-OH->12-C=0
7a-OH->7-C=0
3 a - O H - 3 - C = 0
3 - C = 0 — 3a-OH; 7 - C = 0 - 7 a - O H
Δ1
2CUS
YIELD %
—
37
—
-
10
-
-
-
-
-
60
-
-
-
-
-
-
4
ORGANISM
Streptomyces g r i seus
Proac t inomyces ery thropol is
Corynebacter ium simplex
Alcaligenes faecalis
Bacillus coli
St reptomyces gelat icus
Bacter ium sp.
Corynebacter ium s implex
Corynebacter ium sp.
St reptomyces rubescens
Saccharomyces ce rev i s iae
Escher ich ia coli
Saccharomyces ce rev i s iae
Saccharomyces ce rev i s iae
Streptomyces gelat icus
Alcaligenes faecalis
Clost r idium perfr ingens
Escher ich ia coli
Corynebacter ium s implex
Streptomyces gelat icus
Bacil lus coli
Corynebacter i urn s implex
CONSTANTS m.p.° [a]D
-
185
—
-
195-196
-
-
-
-
-
165
162
-
-
-
-
-
110-115
-
-
—
-
+ 72[ml
-
-
-
-
-
-
+ l l l [ e ]
-
-
-
-
—
+ 12[e]
R E F .
F-235
T-1032
H-367
H-393
F-289
H-366
E-194
H-367
T-974
H-365
E-221
N-675
M-543
K-441
H-366
H-393
N-675
N-675
H-367
H-366
S-899
R-764
215
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C 2 5 H 3 1 0 8 F
^ 2 5 " 3 2 θ 3
C25 H32°5
C25H3205C1F
I ^25"32^7
C 2 5 H 3 4 0 5
C25H3405C1F
C25 H34°6
C 25 H36°5
NAME OF REACTION PRODUCT
9 a - f l u o r o - l l ß , 1 6 a , 1 7 a , 2 1 -te t r ahy droxy -1 ,4 -pr e gna -d iene-3 ,20-dione 1 6 , 2 1 -diacetate
16a-n-butyl-17a-ethinyl-17/3-hydroxy -1 ,4 -androstadiene -3,11-dione
16/3-n-butyl-17a-ethinyl-17/3-hy droxy -1 ,4 -androstadiene -3 , 1 1 , dione
17a,21-dihydroxy-6/3,16a-dimethyl -1 ,4 ,9(11) -p regna-t r i ene -3 ,20 -d ione 2 1 -aceta te
9a -chloro -11/3 -fluor o- 16α, 17a, 21 - t r ihydroxy -6 -methyl - 1 , 5 -pr egnadiene -3,20-dione 16,17-acetonide
l l ß , 1 7 a , 2 1 - t r i h y d r o x y - l , 4 -pregnadiene -3 ,20 -dione 11,21-diaceta te
16a -n -bu ty l -17a ,21 -dihydr oxy -1 ,4 -pr egnadiene -3 ,11 ,20- t r ione
16ß-n -bu ty l -17a ,21-dihydroxy -1 ,4 -pr egnadiene -3 ,11 ,20 - t r ione
16a -n -bu ty l -17a ,21 -dihydroxy -1 ,5 -pr egnadiene -3 ,11 ,20 - t r ione
16j3-n-butyl-17a,21-dihydroxy-1 , 5-pr egnadiene-3 ,11 ,20- t r ione
9a -chloro -11/3 -f luoro- 16a, 17a, 21 - tr ihydroxy -2a -methyl - 5 -p regnene -3 ,20 -dione 16,17-acetonide
14/3,16ß-dihydroxy-3-keto-5/3-20(22)-cardenolide 16-aceta te
16a- t -butyl -11a , 17a, 21 - t r i -hydroxy -1 ,4 -pr egnadiene -3,20-dione
16a- t -bu ty l - l l /3 ,17a , 21 - t r i -hydroxy -1 ,4 -pr egnadiene -3,20-dione
TRANSFORMATION
Δ1
1 Δ
1 Δ
1 Δ
21 -OAc-21 -OH
1 Δ
1 Δ
1 Δ
21-OAc->21-OH
21-OAc-21-OH
21-OAc^21-OH
3 ß - O H - 3 - C = 0
3/3-OAc—3-C = 0
l l a - O H
l l ß - O H
YIELD
% 1
—
—
59
—
—
—
—
2
-
-
—
-
ORGANISM
Corynebac ter ium s implex
Corynebacter ium s implex
Corynebacter ium s implex
Corynebacter ium s implex
Flavobacter ium dehydrogenans
Corynebacter ium s implex
Corynebacter ium s implex
Corynebacter ium s implex
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Flavobacter ium dehydrogenans
Calonect r ia decora
Nigrospora sphaer ica
Calonectr ia decora
Nigrospora sphaer ica
Beauver ia sp .
Glomere l la sp.
Phoma sp.
Phoma sp.
CONSTANTS m.p.° [a]D
158-235 + 22[c | (solvate); 186-188; (solvate)
— —
— —
219-221 +152[c|
— —
— —
— —
— —
242-249 —
- -
- -
— —
- -
R E F .
B-60; B-59
O-701
O-701
N-691
N-691
H-389
N-692
N-692
N-690; 1 N-692
N-690; N-692
N-691
N-677
N-677
N-677
N-677
1-421
C-109
1-422
1-422
216
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL FORMULA
^ 2 5 " 3 6 ^ 6
^ 2 5 " 3 6 ^ 7
C2 5 H4 0 O5
^ 2 β " 3 4 ^ 7
C 2 6 H 3 5 ° 7 F
^26 " 3 6 ^ 6
C 2 6 H 4 0 U 2
^ 2 6 ^ 4 2 ^ 5
C26H4403
C27H2905P
C27H30O5FP
NAME OF REACTION PRODUCT
3/3,14/3,16/3-trihydroxy-5/3-20(22)-car denolide 16-acetate (oleandrigenin)
3/3,12/3,14/3, 16/3-tetrahydroxy-5/3-20(22) -cardenolide 16-acetate
1 6 a - t - b u t y l - l l a , 1 7 a , 2 1 - t r i -hydroxy-5a-pregnane-3 ,20-dione
16a - t -bu ty l - l l / 3 , 17a ,21 - t r i -hydroxy-5a-pr egnane-3 ,20-dione
3/3,6/3, 8/3,14/3-tetrahydroxy-4,20,22-bufatr ienol ide 6-acetate (scil l irosidin)
9 a - f l u o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 -te t rahydroxy-4-pregnene-3,20-dione 16,17-acetonide 21-acetate
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - l , 4 -pr egnadiene -3 ,20 -dione 21 - t r imethylaceta te
2 7 -nor-4 -cholestene - 3 , 2 5 -dione
3a, 12a-dihydroxy-5/3-cholanic acid 12-acetate
A - n o r - 3 , 5 - s e c o - 5 - k e t o -choles tan-3-oic acid
16a, 17a -d ihydroxy-1 ,4 ,6 -pregnat r iene -3 ,20 -dione 16,17-cyclophenylphos-phonate
6a-f luoro-16a, 17a -dihydroxy -1,4-pr egnadiene-3 ,20-dione 16,17-cyclophenyl-phosphonate
TRANSFORMATION
3/3-0 \c-3 /3-OH
12/3-OH
l l a - O H
11/3-OH
3/3-[lf ξ -glucosidel ^3/3-OH
21-OH^21-OAc
ά,Ι^ά-Α +1
3i3-OH->3-C = 0 ; Δ 5 - Δ 4
3-C = 0 - 3 a - O H
cholestenone -> r ing A cleavage
choles terol —» r ing A cleavage
Δ1
Δ1
YIELD %
—
14
—
-
—
15
5-100
85-90
90
60-90
50
15
30
35
70(cr.)
—
14
33(cr.)
t r .
—
ORGANISM
Calonectr ia decora
Nigrospora sphaer ica
Gibberella saubinett i
Beauveria sp.
Glomerel la sp.
Phoma sp.
Phoma sp.
Al te rnar ia sp.
Aspergi l lus sp.
Claviceps purpurea
Paec i lomyces sp.
Pénici l l ium sp.
Pul lu la r ia pullulans
Rhizopus n igr icans
Stachybotrys sp.
Stemphylium sp.
Tr ichoderma glauca
Didymella lycopers ic i
Micrococcus dehydrogenans
Saccharomyces ce rev i s iae
Proac t inomyces erythropol is
Mycobacter ium sp.
Bac te r ium cyclooxydans
Bacter ium cyclooxydans
CONSTANTS m . p . ° [α]Ώ
—
233-238
—
-
—
:
-
-
-
-
-
-
-
239-240
233-236
128
174-175
150
—
—
+ 6[m]
—
-
—
—
-
-
-
-
-
-
-
+136[m]
+103[c]
—
—
—
—
REF.
N-677
N-677
0-699
1-421
C-109
1-422
1-422
S-936a
S-936a
S-936a
S-936a
S-936a
S-936a
S-936a
S-936a
S-936a
H-404
W-1102
E-214
K-442
T-1034
S-930
F-259
F-259
217
TABLE I
T r a n s f o r m a t i o n s by P r o d u c t
EMPIRICAL FORMULA
C 2 7 H3 7 0 6 F
C 27H 3 803
L 2 7 n4o^3
C2 7 H4 0 O5
1 ^27"42^2
1 ^ 2 7 " 4 2 ^ 3
C 2 7 H4 2 0 4
C2 7 H4 2 ° 5
C27H4303N
C27H440
NAME OF REACTION PRODUCT
6 ö - f l u o r o - l l ö , 1 6 ö , 1 7 ö , 2 1 -te t r ahydroxy-4-p regnene-3,20-dione 16 ,17-cyc lo-hexanonide
1,4-diosgadien-3 -one
4-diosgen-3-one
9 -dehydromanogenin
1 lö -hydroxy - 7-ketodiosgenin
4 -cholestene -3 ,6 -dione
22a, 25D-5-spirosten-3/3-ol (diosgenin)
hecogenin
manogenin
7/3, l lö-dihydroxydiosgenin
7/3-hydroxy solasodine
9ö -hydroxy s olasodine
1 lö-hydroxy solasodine
5 ,7-chole Stadien-3/3-01
4-choles ten-3-one
•
TRANSFORMATION
l l ö - O H
3/3-OH-3-C = 0 ; Δ 5 ^ Δ 4 . Δ1
3/3-OH-3-C = 0 ; Δ5 —Δ 4
3/3-glycoside (dioscin)—3β-ΟΗ; 3/3-OH-3-C = 0 ; Δ 5 ^ Δ 4
3/3-glycoside (saponinH3/3-OH
l l ö - O H ; 7/3-OH; 7/3-OH^7-C = 0
3 / 3 - O H - 3 - C = 0 ; Δ 5 ^ Δ 4 . 6-C = 0
3ß-glycoside (dioscinH3/3-OH
3/3-glycoside (saponin)->3/3-OH
3/3-glycoside (saponinH3/3-OH
7ß-OH; l l ö - O H
7/3-OH
9ö-OH
l l ö - O H
7
Δ
3/3-OH-+3-C=0; Δ 5 - Δ 4
YIELD %
~Ί -
—
2
—
5-10
—
5
—
-
-
—
10-15
1
27
1
-
-
—
—
ORGANISM
Colletotr ichum phomoides
Corynebacter ium s implex
Corynebacter ium s implex
Pénic i l l ium chrysogenum
Aspergi l lus sp.
Pénic i l l ium sp.
Helicostylum p i r i fo rme
Mycobacter ium sp.
Aspergi l lus t e r r e u s
Al t e rna r i a sp .
Aspergi l lus sp.
Corynespora casai icola
Pénic i l l ium sp .
Aspergi l lus sp.
Pénic i l l ium sp.
Helicostylum p i r i fo rme
Helicostylum p i r i forme
Helicostylum p i r i fo rme
Helicostylum p i r i fo rme
Azotobacter oxydans
Acetobacter xylinum
Azotobacter oxydans
Bac te r ium cyclooxydans
Corynebac ter ium s implex
CONSTANTS m . p . ° [α]Ό
'
—
-
180-181.5
—
221-225
-
205.5-208
—
-
-
—
263-266
234-238
213-215
200-203
141-143
80-81
-
-
—
—
- 7[cl
—
-137[e]
-
-118[c]
—
-
-
—
- 47[el
- 82[cj
-138[cl
-110[cl
-
+ 87
-
-
R E F .
D-159
N-665
N-665
R-781
K-479
K-479
H-368
S-930
R-781
H-351
K-479
H-351
K-479
K-479
K-479
H-368
S-791
S-791
S-791
H-406; H-407
K-457
H-406; H-407
T-1005
T-1005
218
TABLE I
T rans format ions by Product
EMPIRICAL FORMULA
C27H440
C27H4403
C27H4404
C27H4405
C27H4503N
C27H4504N
C27H460
1 C27H4602
C27H480
jC^HggUglr
NAME OF REACTION PRODUCT
4-choles ten-3-one
ti go gen in
gitogenin
digitogenin
7a-hydr oxytomatidine
9a -hydr oxytomatidine
7a, l la -d ihydroxytomat id ine
5/3-7-cholesten-3/3-ol
5/3-cholestan-3-one
5 -cholestene -3/3,7ξ -diol
5a-c hole s tan-3ß-ol
5/3-cholestan-3/3-ol
16α, 17a-dihydroxy-6ß-methyl -1 ,4 -pr egnadiene -3,20-dione 16,17-(phenyl cyclophosphate)
TRANSFORMATION
3/3-OH->3-C = 0 ;
3/3-glycoside (saponin)^3/3-OH
3/3-glycoside (saponin)^3/3-OH
3/3-glycoside (saponin)->3/3-OH
7a-OH
9a-OH
7a-OH; 11a-OH
Δ5-*5/3-Η
3/3-OH->3-C=0
7ξ-ΟΗ
3-C=0->3/3-OH
Δ5-^5/3-Η
1
Δ
YIELD %
16-44
11-23
-
-
-
34-45
-
-
—
—
-
—
5
< 1
20
50
21
—
65
74
-
ORGANISM
Corynebacter ium sp.
Flavobacter ium m a r i s
Mycobacter ium rhodocrous
Mycobacter ium sp.
Nocardia sp.
Proac t inomyces ery thropol is
Proac t inomyces r o s e u s
Streptomyces sp.
Aspergi l lus sp.
Pénici l l ium sp.
Aspergi l lus sp.
Pénic i l l ium sp.
Bacil lus mace rans
Flavobacter ium sp.
Helicostylum p i r i forme
Helicostylum p i r i forme
Helicostylum p i r i forme
" r a t feces a n a e r o b e s "
P roac t inomyces erythropol is
Proac t inomyces r o s e u s
Saccharomyces ce rev i s iae
" r a t feces anae robes"
fecal bac te r ia
Bac te r ium cyclooxydans
CONSTANTS m . p . ° [α]Ό
80
80
-
-
-
80
-
-
—
—
-
—
238-242d
188-191
266-270d
104-105
61
—
141-142
-
99-101
-
-
-
-
-
-
-
—
—
-
—
- 3.5[c]
—
+ 23[el
+ 54.5
—
—
-
-
-
REF.
C-136
A-21; A-19; A-22 ; B-50
T-1005
S-930
T-1005
T-1031; T-1032
K-474
T-1005
K-479
K-479
K-479
K-479
S-794
S-795
S-791
S-791
S-791
C-133
T-1032
K-474
M-543
C-133
S-914
F-259
219
TABLE I
T r a n s f o r m a t i o n s by Product
EMPIRICAL 1 FORMULA
C29H3506C1
C 29 H 44°8
C29H160
C 2 9 H 4 8 °
C29H520
|c3 0H3 4O7ClP
1 ^3θ"46^7
C30 H44 O9
1 ^30^46^8
j ^32"48^9
C36H54°14
C41H64°13
NAME O F REACTION PRODUCT
6 ö - c h l o r o - l i a , 1 6 a , 1 7 a , 2 1 -te t rahydroxy-4-pregnene-3,20-dione 16 ,17-ace to -phenonide
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide 3 - (L - rhamno-side)
4,22 -s t igmastadien -3 -one
4 - s t igmas ten -3 -one '
5/3-stigmastan-3/3-ol
1 2 o - c h l o r o - l l ß , 1 6 ö , 1 7 α , 2 1 -t e t r ahyd roxy-1 ,4 -p regna -diene-3 ,20-dione 1 6 , 1 7 -(benzyl cyclophosphonate) 21-aceta te
3/3,14/3 -dihydroxy -5/3 -20(22)-cardenolide 3 - [D-cymaro -side]
3ß,5/3,14/3-trihydroxy-19-oxo-20(22) -cardenolide 3- jD-cymaros ide l
3/3,14/3,16/3-trihydroxy-5/3-20(22)-cardenolide 3 -[D-cymaros ide]
3/3,14/3,16/3-trihydroxy-5/3-20(22)-cardenolide 3 -[D-cymaros ide] 16-aceta te
3/3,5/3,14/3-trihydroxy-19-oxo-20(22)-cardenolide 3 -[D-glucosyl -D-cymaros ide]
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide 3 - [digitoxosy 1 -digitoxosyl-digitoxoside] (digitoxin)
TRANSFORMATION
l l a - O H
2 ' - O A c - 2 ' - O H ; 3 ' - O A c ^ 3 ' - O H ; 4 ' -OAc->4 ' -OH
3/3-OH-3-C = 0 ; Δ5 ->Δ4
3/3-OH-3-C = 0 ; Δ 5 ->Δ 4
Δ 5 - 5 β - Η 1
Δ
4 r - O A c - 4 ' -OH
digitoxigenin --3- [D-glucosyl -D-g lucosy l -D-cymaro-side l^digi toxigenin -3- [D-cymaros ide]
strophanthidin -3 -fheptaacetyl-D-glucosyl-D-glucosyl-D-cymaros ide] — strophanthidin 3 -[D-cymaroside]
4 ' -OAc^4-OH; 16/3-OAc-* 16/3-OH
4 ' - O A c - 4 f -OH
D-glucosy l -D-cymaros ide t e t r a c e t a t e - ^ D -g lucosy l -D-cymaro-side
digi toxosyl-digi-toxosy 1 - digitoxoside t e t r aacetate—>digi -toxosy 1 - digitoxosyl-digitoxoside
glucosy 1 - digitoxosyl -digitoxosyl-digi -toxoside—digitoxosyl digitoxosy 1 -digi -toxoside
YIELD
% i
14
19
36
66
40
28
52
3
47
4
18-100
5-95
30-60
20
5-95
ORGANISM
Trichothecium ro seum
F u s a r i u m lini
P roac t inomyces erythropol is
P roac t inomyces ery thropol is
" r a t feces anaerobes '
Bacter ium cyclooxydans
Fusa r ium lini
F u s a r i u m lini
Fusa r ium lini
F u s a r i u m lini
Fusa r ium lini
Fusa r ium lini
Fusa r ium lini
Aspergi l lus sp.
Claviceps purpurea
Paec i lomyces sp .
Pénic i l l ium sp.
CONSTANTS m.p.° [Œ]D
212-221 -
125 -
83 -
126-127 + 23
186-197 -
188-200; -140-158
131-133 -
154-195 —
187-207 —
247-250 —
- -
_ —
R E F .
D-159
T-978
T-1032
T-1032
C-133
F-263
T-978
T-978
T-978
T-978
T-978
T-978
T-978; G-320
S-936a
S-936a
S-936a
S-936a
CHAPTER IV
TAXONOMY
SYSTEM OF CLASSIFICATION
The system of classification used here is designed as an aid to determine the taxonomic position and relationships of the genera, active and inactive, that have been used for the transformations of steroids.
Generally, the same groupings or categories have been used for classifications of bacteria and fungi as have been used for plants. For example,
Kingdom: Plant
Phylum: Fungi (Eumycophyta); typically filamentous organisms lacking chloro-phyll (depend for their food either directly or indirectly on green plants )
Class: Ascomycetes; ultimate reproductive spores produced internally in a saclike cell called ascus. Mycelium septate Basidiomycetes; ultimate reproductive spores produced externally upon a special organ called basidium. Mycelium septate Phycomycetes; mycelium usually aseptate and multinucleate Fungi Imperfecti (Deuteromycetes); artificial grouping of fungi whose sexual stages are not known. They are the imperfect stages of the Ascomycetes and Basidiomycetes
Schizomycetes; true bacteria, single cell, reproduction by fission
Order: Subunit of Class
Family: Subunit of Order
Genus: Subunit of Family
Species: Subunit of Genus (may be further broken down into varieties, strains, and physiological or cultural races)
The classes, orders, families, genera, and species in the various tables are listed alphabetically for convenience and, therefore, may not be in the same sequence as would be found in various published systems of taxonomy.
Table II is a taxonomic listing for reference purposes containing all cultures reported in the literature and U.S. patents through January, 1964. This spectrum of genera encompases all five classes of microorganisms, the Ascomycetes, Basidio-mycetes, Fungi Imperfecti, Phycomycetes, and Schizomycetes, twenty-three out of 49 major orders, 292 different genera, and 1216 different species.
220
SYSTEM OF CLASSIFICATION 221
The most widely screened taxonomic class has been the Fungi Imperfecti. In fact, this is the only class in which all of the orders within a class (four) have been studied. One hundred eleven of the 292 genera listed in Table II and five hundred thirty-four of the 1216 species are members of the Fungi Imperfecti.
The tabulation entitled "Classes and Major Orders of Fungi and Bacteria" r e -ported to transform steroids shows that this ability is rather widespread in the micro-bial world.
This is further emphasized in tabulations entitled "Hydroxylation — Taxonomic Distribution According to Order" and "Hydroxylation — Taxonomic Distribution According to Genus," as well as the distribution of cultures capable of Δ1- dehydro-genation classified to taxonomic order and genus.
As a result, it is quite difficult to draw taxonomic inferences of major signifi-cance at the class or order level.
The differences observed at the genus, species, or strain levels are governed more by the nature of the substrates and the environmental conditions of growth than by taxonomic considerations. These differences can be selected readily by checking the species of the genus in question in Table III "Transformation by Genus."
Of the reported cultures, the group with the narrowest spectrum of activity appears to be the yeasts. Only two genera (of 19 tested), Saccharomyces and Rhodotorula, showed any activity and this was limited to their ability to reduce ke-tones to hydroxyl groups and to reduce double bonds.
An extensive discussion of the reactions listed in the aforementioned taxonomic tables is presented in the section on chemical transformations in Chapter II.
222 IV. TAXONOMY
Classes and Major Orders of Fungi and Bacteria M
Ascomycetes
Dothideales Endomycetales Erysiphales Eurotiales Helotiales Hemisphaeriales Hypocreales Hysteriales Laboulbeniales Myriangiales Pezizales Phacidiales Sphaeriales Taphrinales Tuberales
Basidiomycetes
Agaricales Hymenogastrales Lycoperdales Nidulariales Phallales Sclerodermatales Tremellales Uredinales Ustilaginales
0 + 0 + + 0 + 0 0 + + 0 + + +
+ 0 + 0 0 0 + 0 +
Fungi Imperfecti (Deuteromycetes)
Melanconiales Moniliales Mycelia Sterilia Sphaeropsidales
Phycomycetes
Blastocladiales Chytridiales Ento mo phtho rales Hyphochytriales Lagenidiales Leptomitales Monoblepharidales Muco rales Peronosporales Plasmodiophorales Saprolegniales
Schizomycetes
Actinomycetales Beggiatoales Caryophanales Chlamydobacteriales Eubacteriales Hyphomicrobiales Mycoplasmatales Myxobacteriales Pseudomonadales Spirochaetales
+ + + +
0 0 + 0 0 0 0 + + 0 0
+ 0 0 0 + 0 0 0 + 0
* Arranged alphabetically. +, Reported to transform steroids; 0, not mentioned.
Î Other taxonomic groups which have been reported to transform: algae (Chlorophyta), Order: Chlorococcales; plants (Spermatophyta), Orders: Liliiflorae, Rosales; protozoa (Masti-gophora), Orders: Euglenoidina, Polymastigina.
Hydroxylation — Taxonomic Distribution According to Order
Class and Order
Ascomycetes
Eurotiales Helotiales Hypocreales Pezizales Sphaeriales
Basidiomycetes
Agaricales
Fungi Imperfecti (Deuteromy cetes )
Melanconiales Moniliales Mycelia Sterilia Sphaeropsidales
Phy co my cetes
Ento mophtho rales Mucorales Peronosporales
Schizomycetes
Actinomycetales Eubacteriales Ps eudo mo nadales
a
*.
*
1
~ß
*
* * *
*
* *
2
a ß
*
*
*
* *
* * *
5
a ß
* *
6
a ß
*
*
*
*
* * * *
* *
* *
r
a
* *
*
*
*
r ~ß
*
*
* * *
*
*
8
ß
*
9
a ß
*
*
*
*
* * *
10
ß
*
*
11
a
* * * * *
*
* * * *
* *
*
ß
*
*
* * * *
* *
* * *
12
a
* *
*
*
ß
*
*
* *
*
*
14
a
*
*
*
*
*
* *
15
a
*
*
*
* * *
*
*
ß
*
*
*
* * *
*
*
16
a
*
*
* *
*
* *
ß
*
*
* *
*
*
*
17
a
*
*
*
*
*
18 19 21
*
*
* *
* * *
*
SYST
EM
OF
CL
ASSIFIC
AT
ION
223
224 IV. TAXONOMY
Hydro xylation - Taxonomic Distribution According to Genus
Position and class Order Genus
l t t-OH
Ascomycetes Basidiomycetes Fungi Imperfecti
(Deuteromycetes) Phycomycetes Schizomycetes
10-OH Ascomycetes
Basidiomycetes Fungi Imperfecti
(Deuteromycetes)
Phycomycetes
Schizomycetes
Moniliales
Actinomycetales
Sphaeriales
Moniliales
Mycelia Steriiia
Sphaeropsidales Mucorales
Actinomycetales Eubacteriales
Pénicillium
No cardia
Gnomonia Xylaria
Cladosporium
Rhizoctonia Sclerotium Haplospo relia Absidia Cunninghamella Mortierella Streptomyces Co ry nebacter ium
2a-OH Ascomycetes Basidiomycetes Fungi Imperfecti
(Deuteromycetes) Phycomycetes Schizomycetes
2/3-OH Ascomycetes
Basidiomycetes Fungi Imperfecti (Deuteromycetes)
Phycomycetes
Schizomycetes
Actinomycetales
Sphaeriales
Agaricales Moniliales
Entomophtho rales Mucorales Actinomycetales Eubacteriales
No cardia
Diaporthe Gnomonia Pyrenophora Sclerotinia Corticium Botrytis H elmintho spo r ium Macrosporium Pénicillium Rhizoctonia Thyrospora Conidiobolus Absidia Streptomyces Bacillus Escherichia Serratia
SYSTEM OF CLASSIFICATION 225
Hydroxylation - Taxonomic Distr ibut ion According to Genus (continued)
Posi t ion and c l a s s Orde r Genus
5ûf-OH
Ascomycetes Basidiomycetes Fungi Imperfect i
(Deuteromycetes ) Phycomycetes Schizomycetes
Mucora les
5/3-OH
Ascomycetes Basidiomycetes Fungi Imperfect i
(Deuteromycetes) Phycomycetes
Schizomycetes
6a?-OH
Ascomycetes Basidiomycetes Fungi Imperfect i
(Deuteromycetes) Phycomycetes Schizomycetes
6/3-OH
Ascomycetes
Mucora les
Euro t ia les Hypocrea les
Sphaer ia les
Basidiomycetes Agar ica les
Cokeromyces
Absidia Cunninghamella Mucor Rhizopus
Thielavia Cordyceps Gibberel la Chaetomium Cochliobolus Daldinia Glomere l la Ophiobolus Pyrenophora Xyla r i a Boletus Clavar ia Coriolus Cor t ic ium Dermoloma Hydrophorus I rpex Lenzi tes Leucopaxil lus Naematoloma Naucor ia
226 IV. TAXONOMY
Hydroxylation — Taxonomic Distribution According to Genus (continued)
Position and class Order Genus
6/3-OH (continued) Bas idiomyc êtes
Fungi Imperfecti (Deuteromycetes)
Agaricales
Melanconiales
Moniliales
Phycomycetes
Mycelia Sterilia
Sphaeropsidales
Ento mo phtho rales Mucorales
Schizomycetes Actinomycetales
Eubacteriales
Pellicularia Polyporus Polystictus Poria Colletotrichum Gloesporium Acrostalagmus Arthrobotrys Aspergillus Botrytis Cephalothecium Curvularia Fusarium Gliocladium Helminthospo rium Hyalopus Isaria Nigrospora Pénicillium Piricularia Stysanus Tricoderma Tricophyton Tricothecium Virticillium Rhizoctonia Sclerotium Co nio thy rium Haplosporella Phoma Wojnowicia Basidiobolus Absidia Blakeslea Chaetocladium Choanephora Circinella Cokeromyces Cunninghamella Helicostylum Mortierella Mucor Phycomycetes Rhizopus Syncephalastrum Thamnidium Zygorhynchus Actinoplanes Streptomyces Achromobacter Bacillus
SYSTEM OF CLASSIFICATION 227
Hydroxylation - Taxonomic Distr ibut ion According to Genus (continued)
Posi t ion and c l a s s O r d e r Genus
7 a-OH
Ascomycetes
Basidiomycetes Fungi Imperfect i
(Deute romyc êtes)
Phycomycetes
Schizomycetes
7/3-OH
Ascomycetes Basidiomycetes Fungi Imperfect i
(Deuteromycetes)
Phycomycetes
Schizomycetes
8/3-OH
Ascomycetes Basidiomycetes Fungi Imperfect i (Deuteromycetes )
Phycomycetes Schizomycetes
9a-OH
Ascomycetes Basidiomycetes
Pez iza les Sphaer ia les
Moniliales
Sphaeropsidales
Mucora les
Sphaer ia les Agar ica les Moniliales
Mycelia S te r i l i a Sphaeropsidales
Mucora les
Ac tino my c é ta les
Monil iales
Pez i za Glas inospora Glomere l la Neurospora
Asperg i l lus Curvu la r ia Fusidium Helminthosporium Coniothyrium Diplodia Hel icostylum Mucor Phycomyces Rhizopus
Xyla r ia Psi locybe Aspergi l lus Cephalosporium Cladosporium Pénici l l ium Tr icothec ium Rhizoctonia Diplodia Haplosporel la Absidia Cunninghamella Helicostylum Mucor Rhizopus Syncephalas t rum Proac t inomyces
(Nocardia) S t reptomyces
Ce rcospo ra
Sphaer ia les Neurospora
228 IV. TAXONOMY
Hydroxylation -Taxonomic Distribution According to Genus (continued)
Position and class Order Genus
9Q?-OH (continued) Fungi Imperfecti
(Deuteromycetes)
Phy corny c êtes
Schizomycetes
Moniliales
Sphaeropsidales Mucorales
Actino my c étales
Eubacteriales
Ps eudo mo nadal es
Cercospora Curvularia Cylindrocarpon Ascochyta Absidia Circinella Cunninghamella Helicostylum Mucor My co bac ter ium Nocardia Streptomyces Arthrobacter Bacterium Corynebacterium Pseudomonas
9/3-OH Ascomycetes Basidiomycetes Fungi Imperfecti
(Deuteromycetes) Phycomycetes Schizomycetes
10/3-OH Ascomycetes Basidiomycetes Fungi Imperfecti
(Deuteromycetes )
Phycomycetes Schizomycetes
Moniliales
Mucorales
Botrytis Curvularia H elmintho spo r ium Rhizopus
l la-OH Ascomycetes t Eurotiales
Helotiales Hypocreales
Pezizales Sphaeriales
Carpenteles Sclerotinia Calonectria Cordyceps Pyrenema Chaetomium Cochliobolus Daldinia Didymella Glomerella Guignardia Ophiobolus Pyrenophora Xylaria
SYSTEM OF CLASSIFICATION 229
Hydroxylation-Taxonomic Distribution According to Genus (continued)
Position and class Order Genus
11a?-OH (continued) Basidiomycetes Agariales
Fungi Imperfecti (Deuteromycetes)
Melanconiales
Moniliales
Mycelia Sterilia
Boletus Clavaria Conocybe Corticium Cortinellus Der mo lo ma Ganoderma Hygrophorus Leucopaxillus Pellicularia Polyporus Polystictus Psilocybe Stropharia Colletotrichum Coryneum Gloesporium Pestalotia Acrostalagmus Arthrobotrys Aspergillus Beauvaria Botrytis Candelospora Cephalothecium Cercospora Cladosarum Dactylium Didymocladium Fusarium Helminthosporium Hyalopus Isaria Metarrhizium Mycogone Myrothecium Nigrospora Pénicillium Piricularia Scopulariopsis Spicaria Sportrichum Stachylidium Stysanus Tricoderma Trichophton Trichothecium Verticillium Rhacodium Rhizoctonia Sclerotium
230 IVc TAXONOMY
Hydroxylation - Taxonomic Distribution According to Genus (continued)
Position and class
l la-OH (continued) Fungi Imperfecti
(Deuteromycetes)
Phycomycetes
Order Genus
Sphaerops idales
Entomophthorales
Mucorales
Schizomycetes Eubacteriales
Botryodiplodia Coniothyrium Diplodia Phoma Phomopsis Wojnowicia Basidiobolus Conidiobolus E nto mophtho r a Absidia Blakeslea Choanephora Circinella Cunninghamella Lichtheimia Mucor Mycocladus Phy corny ces Rhizopus Syncephalastrum Thamnidium Tieghemella Zygorhynchus Achromobacter Bacillus Escherichia
11/3-OH Ascomycetes Basidiomycetes
Fungi Imperfecti (Deuteromycetes)
Helotiales Agaricales
Melanconiales
Moniliales
Mycelia Sterilia
Sclerotinia Corticium Omphalia Pellicularia Colletotrichium
Arthrobotrys Botrytis Cercospora Curvularia Epicoccum Isaria Pénicillium Spicaria Spondy lo cladium Stachylidium Stigmina Tricophyton Tricothecium Verticillium Rhizoctonia Sclerotium
SYSTEM OF CLASSIFICATION 231
Hydroxylation - Taxonomic Distribution According to Genus (continued)
Position and class Order Genus
11/3-OH (continued) Fungi Imperfecti
(Deuteromycetes)
Phycomycetes
Schizomycetes
Sphaeropsidales
Mucorales
Peronosporales Actinomycetales Eubacteriales
Ps eudo mo nadal es
Chaetomella Coniothyrium Dothichiza Phoma Pycnosporium Rhodos eptoria Absidia Blakeslea Choanephora Circinella Cunningham ella Lichtheimia Rhizopus Sync ephalas tr urn Thamnidium Tieghemella Pythium Streptomyces Bacillus E scher ichia Proteus Pseudomonas
12o?-QH
Ascomycetes Bas idiomyc êtes Fungi Imperfecti
(Deuteromycetes)
Phycomycetes Schizomycetes
12/3-OH Ascomycetes
Bas idiomyc êtes Fungi Imperfecti
(Deuter o my c êtes )
Phycomycetes Schizomycetes
14a-OH
Melanconiales
Moniliales
Sphaeropsidales Mucorales
Hypocreales
Agaricales Melanconiales
Moniliales
Sphaeropsidales Mucorales
Colletotrichum
Aspergillus Cercospora Wojnowicia Thamnidium
Calonectria Gibberella Psilocybe Colletotrichum
Fusarium Nigrospora Tricothecium Coniothyrium Helicostylum
Ascomycetes Sphaeriales Pleospora
232 IV. TAXONOMY
Hydroxylation — Taxonomic Distribution According to Genus (continued)
Position Order Genus
14Q?-OH (continued) Basidiomycetes
Fungi Imperfecti (Deuteromycetes)
Phycomycetes
Schizomycetes
Agaric ales
Moniliales
Sphaeropsidales Mucorales
Ac tinomyc étales Eubacteriales
Coriolus Naematoloma Pellicularia Polyporus Poria Cercospora Chrysosporium Curvularia Helminthosporium Stachylidium Stemphylium Tricothecium Wojnowicia Absidia Circinella Cunningham ella Helicostylum Mucor Sync ephalast rum Mycobacterium Achromobacter Bacillus
15a?-OH Ascomycetes
Basidiomycetes Fungi Imperfecti (Deuteromycetes)
Phycomycetes Schizomycetes
15/3-OH Ascomycetes
Hypocreales
Sphaeriales Agaricales Melanconiales
Moniliales
Mycelia Sterilia Mucorales Ac tinomyc étales
Helotiales Sphaeriales
Calonectria Gibberella Glomerella Hypholoma Colletotrichum
Aspergillus Curvularia Fusarium Helminthosporium Hormodendrum Nigrospora Pénicillium Rhizoctonia Rhizopus Streptomyces
Sclerotinia Xylaria
SYSTEM OF CLASSIFICATION 233
Hydroxylation - Taxonomic Distribution According to Genus (continued)
Position Order Genus
15/3-OH (continued) Basidiomycetes
Fungi Imperfecti (Deuteromycetes )
Phycomycetes
Schizomycetes
Agaricales
Moniliales
Mycelia Sterilia Sphaeropsidaies
Mucorales
Eubacteriales
Coriolus Lenzites Polyporus Poria Botrytis Cercospora Crinsporium Helminthosporium Pénicillium Spicaria Sclerotium Diplodia Phoma Absidia Phycomyces Syncephalastrum Bacillus
lto-OH Ascomycetes
Basidiomycetes Fungi Imperfecti
(Deuteromycetes )
Phycomycetes Schizomycetes
Hypocreales Sphaeriales
Melanconiales Moniliales
Sphaeropsidaies
Actinomycetales
Eubacteriales
Hypomyces Didymella Gnomonia Mycosphaerella
Pestalotia C ephalospor ium Sepedonium Staganospora Staurophoma Wojnowicia
Nocardia Streptomyces Bacillus
Ascomycetes Bas idiomyc êtes Fungi Imperfecti
(Deuteromycetes )
Phycomycetes
Schizomycetes
Helotiales Agaricales Melanconiales Moniliales
Sphaeropsidaies Mucorales
Eubacteriales
Sclerotium Corticium Colletotrichum C ephalospor ium Curvularia Wojnowicia Cunninghamella Helicostylum Bacillus
y>e-0H
234 IV. TAXONOMY
Hydroxylation - Taxonomic Distribution According to Genus (continued)
Position Order Genus
17a-OH
Ascomycetes
Bas idiomyc êtes Fungi Imperfecti
(Deuteromycetes)
Eurotiales Hypocreales Sphaeriales
Agaricales Moniiiales
Phy corny c êtes Schizomycetes
18dQ_H
Ascomycetes Bas idiomyc êtes Fungi Imperfecti
(Deuteromycetes ) Phycomycetes Schizomycetes
19-OH
Ascomycetes Basidiomycetes
Fungi Imperfecti (Deuteromycetes)
Phycomycetes Schizomycetes
Moniiiales
Agaricales
Thielavia Melanospora Cucurbitaria Leptosphaeria Lophotrichus Sporormia Naucoria Acrospeira Aspergillus Cephalothecium Dactylium Scopulariopsis Sepedonium Tricoderma Tricothecium
Cercospora
Corticium Hypochnus Pellicularia
21rOH
Ascomycetes
Basidiomycetes
Helotiales Sphaeriales Agaricales
Schlerotinia Ophiobolus Psilocybe
IV. TAXONOMY 235
Hydroxylation — Taxonomic Distribution According to Genus (continued)
Position and class Order Genus
21-OH (continued
.Fungi Imperfecti (Deuter omyc êtes)
Phycomycetes Schizomycetes
Melanconiales
Moniliales
Sphaeropsidales
Colletotrichum
Aspergillus Cercosporella Kabatiella Coniothyrium Hendersonia Wojnowicia
236 IV. TAXONOMY
A1-Dehydrogenation — Taxonomic Distribution According to Genus
Class Order Genus
Ascomycetes
Basidiomycetes
Fungi Imperfecti (Deuteromycetes)
Phycomycetes Schizomycetes
Spermatophyta (plant) Zoomastigina (protozoa) [Mastigophora]
Hypocreales
Sphaeriales
Agaricales
Ustilaginales Melanconiales
Moniliales
Mycelia Sterilia Sphaeropsidales Muco rales Actino my c étales
Eubacteriales
Pseudomonadales
Liliiflorae Polymastigina
Calonectria Hypomyces Chaetomium Didymella Ophiobolus Corticium Stereum Graphicola Gloeosporium Septomyxa Alternaria Cylindrocarpon Fusarium Gliocladium Helmintho spo rium Ramularia Volutella Rhizoctonia Pycnodothis Absidia Actinoplanes Mic ro mo no spo r a Mycobacterium Mycococcus Nocardia Aerobacter Arthrobacter Azotobacter Bacillus Bacterium Corynebacterium Flavobacterium Micrococcus Serratia
Acetobacter Azotomonas Protaminobacter Pseudomonas Xanthomonas Sansevieria Trichomonas
TABLE I I
T a x o n o m y to Spec ies
237
CLASS
Ascomycetes
ORDER
Endomycetales
Euro t ia les
Helotiales
Hypocreales
Myriangiales
FAMILY
Endomycetaceae
Saccharomycetaceae
Eurot iaceae
Gymnoscaceae
Helotiaceae
Hypocreaceae
Myriangiaceae
GENUS
ß y s s o c h l a m y s
Debaryomyces
Dilplodasus
Endomyces
E r e m a s c u s
Eremothec ium
Hansenula
Nadsonia
P ich ia
Saccharomycodes
Schizosaccharomyces
His toplasma
Saccharomyces
Al lescher ia
Thielavia
Carpente les
Sclerot inia
Calonect r ia
Cordyceps
Gibberel la
Hypomyces
Melanospora
Neocosmospora
Elsinoe
SPECIES
nivea 1
hansenii
albidus
l indneri
albus
ashbyii
anomala
fulvescens
membranaefac iens
ludwigii
octosporus
capsulatum
cerev i s iae el l ipsoideus fragi l is lac t is pas to r ianus
boidii
basicola t e r r i c o l a
javanicus
all i i fructicola fluctigena l iber t iana sc l e ro t io rum
decora
mi l i t a r i s
baccata cyanea fujikuroi saubinett i zeae
aurant ius haematococcus solani
pa ra s i t i ca
vasinfecta
ampelina fawcetti
238
TABLE M
T a x o n o m y to Spec ies
CLASS
Ascomycetes
ORDER
Pez iza l e s
Sphaeriales
FAMILY
Hellvellaceae
Pez izaceae
Cera tos tomaceae
Chaetomiaceae
F ime ta r i aceae
Sphaer iaceae
GENUS
Morchella
Pez iza
Py rone ma
Cera tos tomel la
Chaetomium
Neurospora
Cochliobolus
Cucurbi tar ia
Daldinia
Diaporthe
Didymella
Gelas inospora
Glomerel la
Gnomonia
Guignardi
Leptosphaer ia
Lophotrichus
Mycosphaerel la
Ophiobolus
SPECIES
c r a s s i p e s
species
confluens
f imbriate (fimbriata)
cochloides funicolum globosum species succineum
c r a s s a sitophila spec ies
miyabeanus
laburni
concentr ia (concentrica)
numurai
ly coper s ic i vodakii
t e t r a s p o r a
cingulata fluctigena fusaroides glycines gosypii
(gossypii) lagenarium major mume phacidiomorpha rubicola
cingulata e r rabunda e ry th ros toma fimicola f ragar iae
camel l iae
maculans
mar t in i
hori i l a tebrosa
g ramin i s herpo t r ichus he te ros t rophus
TABLE I I
Taxonomy to Spec ies
239
CLASS
Ascomycetes
1 Basid iomycetes
ORDER
Sphaer ia les
Taphr ina les
Agar ica les
FAMILY
Sphaer iaceae
Taphr inaceae
Agar icaceae
GENUS
Ophiobolus
Ophiostoma
P leospora
Pyrenophora
Rosse l l in ia
Sordar ia
Sporormia
Venturia
Xylar ia
Taphrina
Agar icus
Agrocybe
Amanita
Armi l l a r i a
Cantharel lus
Clitocybe
Collybia
Conocybe
Coprinus
Cor t ina r ius
Cort inel lus
Dermoloma
SPECIES
miyabeanus 1 sat ivus 1 spec ies 1
catanianum
gaeumanni
g reminea
neca t r ix
spec ies
fasciculata leporina minima montana pol lacci i
p i r m a (pirina)
polymorpha spec ies
deformans pruni
c a m p e s t r i s edulis rodmani i
ace r ico la
m u s c a r i a porphyr ia
mellae
c ibar ius
adi rondackensis clavipes odor a spec ies
dryophila velut ipes
si l igenoides
a t romenta r ius (a t ramentar ius)
sobil i ferus
evernius
shii take
spec ies
240
TABLE I I
T a x o n o m y to S p e c i e s
CLASS
Basidiomycetes
ORDER
Agar ica ies
FAMILY
Agar icaceae
GENUS
Gymnopilus
Hebeloma
Hygrophorus
Hypholoma
Lentinus
Lentodium
Lepiota
Leucopaxillus
Lyophyllum
Marasmius
Mycena
Naematoloma
Naucoria
Omphalia
Panaeolus
Panel lus
Paxi l lus
Pholiota
P leuro tus
Pluteus
Psi locybe
Russula
Schizophyllum
Stropharia
SPECIES
junenius spec ies
s inapizans
conicus
species
vulpinus
squamosum
molybdites naucina p r o c e r a rachodes
paradoxus
aggregatum
s iccus
strobil inoides
subla tera t ium
confragosa
t ra luc ida
papil ionaceus
st ipt icus
involutus verna l i s
adiposa squar roso ides
japonicus os t r ea tus
granular is
cae ru lescens caeru i ipes mexicana semper viva
del icans
commune
cubensis normandii
TABLE I I
T a x o n o m y to S p e c i e s
241
CLASS
ßas id iomyce tes
ORDER
Agar ica les
FAMILY
Agar icaceae
Boletaceae
Clavar iaceae
Hydnaceae
Hypochnaceae
Polyporaceae
GENUS
Tr icholoma
Tubar ia
Xeromphal ina
Boletinus
Boletus
Clavar ia
Echinodontium
Irpex
Hypochnus
Coriolus
Fomes
Ganoderma
Lenzi tes
Polyporus
Polys t ic tus
P o r i a
T r a m e t e s
SPECIES
nudum 1 spec ies
conspe r sa
tenuipes 1
p ic tus
acidus 1 amer i canus luteus
mucida 1
tsugicola
consors lacteus
centrifugum sasak i
vers ico lor
pinicola robs tus spec ies
applam (applanatum)
abie t ina bebulina
(betulina) s ty rac ina
abiet inus b ruma l i s caeru leoporus cinnabarinus conchifer frondosus pubescens rad ica ta squamosus sulphur eus tul ipiferus
c innabar ius h i r s tu s polyzonus sanguineus ve r s i co la ve r s ico lo rpus
cocos spec ies vapora r i a
dickinsi i pini
242
TABLE I I
Taxonomy to Spec ies
CLASS
Basidiomycetes
Fungi Imperfect i (Deuter omycete s )
ORDER
Agar ica les
Lycoperdales
T r e m e l l a l e s
Ust i laginales
Melanconiales
FAMILY
Thelephoraceae
Lycoperdaceae
Aur icu lar iaceae
Graphiolaceae
Usti laginaceae
Melanconiaceae
GENUS
Cort ic ium
Pe l l i cu la r i a
Stereum
To mente lia
Lycoperdon
Helicobasidium
Graphiola
Ustilago
Colletotr ichum
Coryneum
Gloeosporium
Pes ta lo t i a
Septomyxa
Sphaceloma
SPECIES
centrifugum centrifugus graminum mic rosc le ro t i a prac t ico la roefs i i sa lmonicolar sasaki i soiani species vagium vagum
filamentosa
fasciatum induratum
species
umbrinum
mompa
cylindrica
zeae
ant i r rh in i de r r i d i s gloeosporioides lindemuthianum phomoides p is i s p e c i e s
cardinale
cyclaminis foliicolum kaki laet icola ol ivarum
diospyri foedans funerea royenae
aescui i affinis corni sal ic ina tu lasuei
spec ies
243
TABLE I I
T a x o n o m y to S p e c i e s
CLASS
Fungi Imperfect i (Deuteromycetes)
ORDER
Moniliales
FAMILY
Cryptococcaceae
Demat iaceae
GENUS
Candida
Pa rendomyces
Pseudomycoderma
Ti l le t iops is
Ac rospe i r a
Alter na r i a
Cercospora
Chala ra
Cladosporium
Corynespora
SPECIES
guil l iermondii k ruse i pu l che r r ima ut i l is
a s t é ro ïdes
l i ' ac ina
levis
batat icola c i t r i kikutiana pass i f lorae spec ies
apii bat icola calotropidis canescens chenopodii c ladosporioides cruenta diazu fusca hibsci-cannabini i ta l ica kaki kikuchii lagenarum mac rospo ra malvacea rum medicaginis melongenae melonis musae m u s a r u m nicotianae oryzae ro s i co l a sc i rp ico la s e s a m i ta iwanensis vaginae violae zebr ina zinniae
my coder ma
c ladospor iodes fulvam
(fulvum) herbarurn r e s i n a e spec ies
casa i icol i
miso
244
TABLE I I
T a x o n o m y to S p e c i e s
CLASS
Fungi Imperfecti (Deuteromycetes)
ORDER
Moniliales
FAMILY
Demat iaceae
GENUS
Curvular ia
Cylindrocephalum
Dematium
Fumago
Fusic ladium
Hel icoceras
Helminthosporium
Hemispora
Hormodendrum
Humicola
Macrospor ium
Mar gar ino my ce s
SPECIES
brachyspora falcata fallax geniculata inaequalis lunata maculans oryzae pal lescens species t e t r a m e r a trifolii uncinata
aureum
pullulans
spec ie s
diospir i
oryzae 1
avenae 1 br izae buchloes coices
(coicis) gramineum i r r egu l ä r e kusanoi 1 l ee r s i i leptochloae maydis nodulosum oryzae panic i -mel iace i
(miliacei) sat ivum se ta r i ae s igmoideum species t e r e s t r i t i c i -vu lgar is turc icum velur inam
(velutinum) zizaniae 1 zonatum
rogosa
olivaceum pedrosoi vir ide
g r i sea
(grisae)
bataticola
spec ies
TABLE I I
T a x o n o m y to S p e c i e s
245
CLASS
Fungi Imperfect i (Deuter omycetes)
ORDER
Moniliales
FAMILY
Demat iaceae
,TDermatophytesT'
Moniliaceae
GENUS
Nigrospora
Phialophora
Pul lu la r ia
Spondylocladium
Stachybotrys
Stachylidium
Stemphylium
Stigmina
Thyrospora
Epidermophyton
Acremonium
Acros ta lagmus
Ar throbot rys
Aspergi l lus
SPECIES
oryzae 1 spec ies sphaer ica 1
v e r r u c o s a
pullulans spec ies
aus t r a l e xylogenum
spec ies
bicolor theobromae
bot ryosum spec ies
platani
a s t r aga l i
f loccasum
potronii
albus
conoides dactyloides musi formis superba
aculeatus a l l iaceus amste lodami a s p e r e s c e n s as t ianus a t ropurpureus au reus aur icomus avenaceus awamor i batatae b rev ipes butyracea caes ie l lus caespi tosus candidus ca rbonar ius ca rneus cheval ier i c innamomeus c i t r i c i t r i spo rus clavatus conicus echinulatus effusus elegans f ischer i
246
TABLE I I
T a x o n o m y to S p e c i e s
CLASS ORDER FAMILY GENUS SPECIES
Fungi Imperfecti (Deuter omycetes)
Moniliales Moniliaceae Aspergi l lus flavipes flavus fonsecaeus fumigatus giganteus glaucus grac i i i s gymnosardae he rba r io rum inuii i taconicus janus japonicus kanagaw -aens is kawachii luchuensis mangini melleus minimus
(minutus) miyakoensis moll is montevidensis nakazawai nidulans niger ni veo-glaucus niveus ochraceus oryzae ost ianus panamens is pa ra s i t i cus penici l loides phoenicis p ro l i fe rans pseudoglaucus pulverulentus quadri l ineatus r ehmi i r epens r e s t r ictus ruber rugulosus sai toi s c l e ro t io rum sojae s p a r s u s spec ies sulphureus sydowi t a m a r i i t e r r e u s t e r r i c o l a unguis usami i us tus va r i ans var iecolor ve r s ico lo r violaceo -fuscus wentii
TABLE I I
Taxonomy to Species
247
CLASS
Fungi Imperfect i (Deuter omycetes)
ORDER
Moniliales
FAMILY
Moniliaceae
GENUS
Beau ver ia
Bot ry t i s
Candelospora
Cephalosporium
Cephalothecium
Cercospore l l a
Chrysospor ium
Cladosarum
Core throps i s
Cr inspor ium
Dactylium
Didymocladium
Fusidium
Geotr ichum
Gliocladium
Hyalopus
Meta r rh iz ium
Monilia
Monosporium
Mycogone
Oidium
Oospora
Paec i lomyces
SPECIES
bass iana 1 spec ies 1
c ine rea fabae 1 paeoniae 1 rep tons 1 spectabi l i s 1 spec ies 1
penici l loides 1
ac remonium a s p e r u m 1 spec ies 1 subver t ic i l la tum 1
r o s e u m 1
herpotr ichoides
luteium
olivaceus (olivaceum)
ho mini s
panorum
dendroides
t e rna tum
spec ies
lact is
catenulatum del iquescens luteolum r o s e u m spec ies
nopporoensis
anisopliae spec ies
spec ies
ap iospe rmum
jaepi i
s p e c i e s
aurant i i l ac t i s
spec ies var i to i
248
TABLE I I
T a x o n o m y to S p e c i e s
CLASS ORDER FAMILY GENUS SPECIES
Fungi Imperfecti (Deuteromycetes)
Moniliales Moniliaceae Pénic i l l ium aculeatum adametzi albidum aspe rum a t ramentosum aurant io -violaceum aurant io-v i r ens avellaneum biforme brefeldianum brevi -compactum camember t i canescens casei caseicolum char les i i chermes inum chrysogenum c i t reo-v i r ide ci t r inum claviforme clavigerum commune corylophilum corymbiferum crus tosum cyaneofulvum cyaneum cyclopium daleae decumbens digitatum d iversum duponti egyptaceum ehrl ichi i expansum fellutanum frequentans funiculosum fuscum gladioli godlewskii granulatum helicum herquei humuli implicatum islandicum i tal icum janthinellum javanicum jenseni i kapuscinskii lanoso-coeruleum lanoso-gr i seum lanoso-vir id i lanosum lavendulum lovitum lilacinum lividum luteum
TABLE 11
T a x o n o m y to S p e c i e s
249
CLASS
Fungi Imperfect i ( Deuter o my c êtes)
ORDER
Moniliales
FAMILY
Moniliaceae
GENUS
Pénic i l l ium (continued)
SPECIES
P i r i c u l a r i a
mar t ens i i melearg inum melinii miczynskii mult icolor nalgiovensis namyslowskii n igr icans notatum novae -zeelandii ochraceum ochro -ch lo rum ol ivino-vir ide oxalicum pal i tans pal l idum parvum patulum phoenicum p i s ca r ium psi t tac inum puberulum pulvi l lorum purpurescens purpurogenum pusi l lum rac ibo r sk i i r a i s t r i c k i i r e s t r i c t u m r e s t r i c u l o s u m rol fs i i roquefort i r o seo -pu rpu r eum r u b r u m rugulosum sc l e ro t io rum s impl i c i s s imum soli tum soppi spec ies sp icul i sporum spinulosum stecki i s toloniferum s t r i a tum subal te r i t ium t a r d u m ter l ikowski t e r r e s t r e thomii t rzeb insk i i turbatum ur t i cae var iabile vermicu la tum ver rucu losum vinaceum vi r id ica tum waksmanni wortmanni
oryzae
250
TABLE I I
Taxonomy to Spec ies
CLASS
Fungi Imperfect i (Deuteromycetes)
ORDER
Moniliales
FAMILY
Moniliaceae
Rhodotorulaceae
Sporobolomycetaceae
Stilbaceae
Torulopsidaceae
GENUS
Ramula r i a
Sarc inomyces
Scopulariopsis
Sepedonium
Spicaria
Sporotr ichum
Ster igmatocys t i s
T r i chode rma
Trichophyton
Tr icothecium
Tr i t i r ach ium
Vert ic i l l ium
Rhodotorula
Sporobolomyces
I sa r i a
Stysanus
Kloeckera
SPECIES
robusta
c rus taceum
amer i cana brevicaul is
ampul losporum ch rysospe rmum
s impl ic i s s ima spec ies violacea v i r idans
a s t é ro ïdes bombycinum epigaeum gougeroti sul furescens
japonica
album glaucum koningi l ignorum nigrovi rens spec ies v i r ide
concentr icum
ar rhenopum candi du m cys tospor ium domest icum luteum p lasmoparae polybrochum r o s e u m
pu ru reum
a lbo -a t rum dahliae malthousii nieveostxatosum spec ies theobromae
glutinis g rac i l i s longiss ima
r o s e u m
far inosa
médius
apiculata
TABLE I I
Taxonomy to Spec ies
251
CLASS ORDER FAMILY GENUS SPECIES
Fungi Imperfect i (Deuteromycetes)
Moniliales Torulopsidaceae
Tuber cu la r iaceae
Torula
Toru lops is
Cylindrocarpon
Epicoccum
F u s a r i u m
spec ies
ae r i a Candida
radic icola
humicola neglectum oryzae purpurascens spec ies yuccae
aquaeductum a r t h o c e r a s aspidioti avenaceum bata ta t is bulbigenum buxicoia caucas icum cocophilum coeru leum concolor cu lmorum d imerum d ive r s i sporum equiset i expansum gibosum gigas g raminea rum he rbe rum he te rosporum javanicum la te r i t ium lini lycopers ic i m a c r o c e r a s mer i smoides m i c r o c r e a moniliforme nivale niveum niveus o r thoce ra s oxysporum poae pruni redolens r o s e u m sambucinum sa rcochroum semi tec tum solani spec ies sphaer iae sporo t r iche i la sporot r ichio ides sulphureum udum vasinfectum
252
TABLE I I
T a x o n o m y to S p e c i e s
CLASS
Fungi Imperfecti (Deuteromycetes)
ORDER
Moniliales
Mycelia Ster i l ia
Sphaeropsidales
FAMILY
Tubercular iaceae
No Family
Sphaerioidaceae
GENUS
Kabatiella
Myrothecium
Volutella
Rhacodium
Rhizoctonia
Sclerot ium
Ascochyta
Botryodiplodia
Chaetomella
Coniothyrium
Diplodia
Dothichiza
Haplosporel la
Hendersonia
Phoma
Phomopsis
Pycnodothis
Pycnospor ium
Rhodoseptoria
Stagonospora
Staurophoma
Wojnowicia
SPECIES
phoradendr i
ro r idum spec ies
ci l iata
ce l la re
ferrugena solani species
coffeicolum hy drop hi lu m oryzae rolfs i i
favae linicola pinadella viciai
theobromae
oblonga raph ige ra
diplodiella hei lebori helleborine spec ies
nata lens is tuber icola
ferruginosa
spec ies
a b e r r a n s acicola herpot r icha phragmi t i s rubi
spec ies
c i t r i
spec ies
species
spec ies
cur t i s i i
spec ies
g ramin i s
TABLE I I
Taxonomy to Spec ies
253
CLASS
Phycomycetes
ORDER
Entomophthorales
Mu cor aie s
FAMILY
ßas id iobolaceae
Empusaceae
Entomophthoraceae
Choanephoraceae
Cunninghameoaceae
Mor t ie r ie l l aceae
Mucoraceae
GENUS
ßas id iobolus
Entomophthora
Conidiobolus
Choanephora
Cunninghame 11a
Mort ier e lia
Absidia
Actinomucor
Blakes lea
Circ inel la
Cokeromyces
Lichtheimia
SPECIES
r a n a r u m
coronata 1
spec ies
cucurb i ta rum
africana albidia bainier i b lakes leeana echinata echinulata elegans homothall ica r a m o s a spec ies ver t ic i l la ta
alpina bainier i candelabrum isabel l ina marburgens i s ol igospora polycephala pusi l ia tuberosa zonata
coerulea cyl indrospora glauca hyalospora orchid is r a m o s a r e g n i e r i r epens spec ies
corymbosus r epens
t r i s p o r a
muscae s implex spec ies syndowi umbel la ta
r ecu rva tus
corymbifera r a m o s a
254
TABLE I I
T a x o n o m y to S p e c i e s
CLASS ORDER FAMILY GENUS SPECIES
Phycomycetes Mucorales Mucoraceae Mucor
Mycocladus
P a r a s i t e l l a
Phycomyces
Rhizopus
adr ia t icus adventit ius angul isporus berol inens is buntingii chr i s t i anens i s c i rc inel lo ides corymbifer d imorphosporus d i spe r sus dubius e rec tus genevensis globosus glomerula gr iseocyanus guil l iermondii h iemal is humicola
(humicolus) humilis hypochninus javanicus mandshuricus mic rosporus mucedo muro rum pa ras i t i cus p i r i fo rmis plumbeus pusi l lus r a c e m o s u s ramannianus rouxianus rouxii s implex solani spec ies sphaerospora spinosus stolonifer va r ians vuil lemini
hyalinus
s implex
blakesleeanus nitens pi rot t ianus spec ies theobromatus
a r r h i z u s cambodjae chinensis chiuniang cohnii de le mar fo rmosens i s
(formosaensis) japonicus
TABLE I I
T a x o n o m y to S p e c i e s
255
CLASS
Phycomycetes
1 Schizomycetes
ORDER
Mucorales
Pe ronospo ra l e s
Act inomycetales
FAMILY
Mucoraceae
Pi lobolaceae
Thamnidaceae
Pythiaceae
Act inomycetaceae
GENUS
Rhizopus (continued)
Syncephalas t rum
Syncephalis
Thamnidium
Tieghemel la
Zygorhynchus
P i lair a
Chaetocladium
Helicostylum
Phytophthora
Pythium
Nocardia
SPECIES
javanicus 1 kansho 1 kasanens i s 1 n igr icans 1 niveus nodosus 1 oryzae pseudochinensis pygmaeus ref lexus shangaiens is
(shanghaiensis) spec ies stolonifer 1 suinus ' 1 tonkinensis t r i t i c i
c incereum (cinereum)
r a c e m o s u m spec ies
nodosa ref lexa
elegans
coerulea cyl indrospora hyalospora orchidis r epens spinosa t ieghemii tu rkes tan ica
he te rogamus moe l l e r i
anomala
brefeldi i
p i r i forme spec ies
c i t rophthora p a r a s i t i c a
ul t imum
as t e ro ides aurant ia blackwelli i b raz i l i ens i s coel iaca convoluta coral i ina e ry thropol i s farcinica formica
256
TABLE I I
T a x o n o m y to S p e c i e s
CLASS ORDER FAMILY GENUS SPECIES
Schizomycetes Actinomycetales Actinomycetaceae Nocardia (continued)
Proac t inomyces
Actinop lanaceae
Mycobacter iaceae
Actinoplanes
Mycobacter ium
Streptomycetaceae
Mycococcus
Streptomyces
gardner i globerula i tal ica leishmanii maculata madurae mexicanus minima opaca paraffinae polychromogenes r e s t r ictus r u b r a salmonicolor spec ies
act inomorphus a g r e s t i s aquosus coel iacus crystal lophagus erythropol is globerulus minimus paraffinae polychromogenes r e s t r ictus r o s e u s rubroper t inc tus spec ies
mi s sour i ens i s spec ies
album berol inense butyr icum chelonei choles terol icum flavum fortuitum friedmannii hyalinum lact icola luteum phlei r anae rhodochrous rubroper t inc tum rub rum salmonicolor smegmat i s spec ies thamnopheos tuberculos is
spec ies
albidoflavus albidus a lbosporeus albus annulatus
TABLE I I
T a x o n o m y to S p e c i e s
257
CLASS
Schizomycetes
ORDER FAMILY
Actinomycetales St reptomycetaceae
GENUS
Streptomyces
Micromonospora
SPECIES
antibioticus argenteolus aureofaciens a u r e u s bikiniensis bobilae cal ifornicus celluloflavus c h a r t r e u s i s chrysomal lus coelicolor d ias ta t icus d ias ta tochromogenes endus e ry th r eus exfoliatus f imicar ius flaveolus f lavogriseus fradiae fulvissimus gelat icus globisporus globosus g r i seoca rneus g r i seo lus g r i seus hals tedi i hydrogenans hygroscopius lavendulae l ipmanii mediocidicus microflavus n i t rosporeus ol ivaceus ol ivochromogenus pa rvus purpureochromogenus r i m o s u s roseochromogenus ruber rubescens rub r i r e t i cu l i rubroocyanodiastat icus] r u t g e r s e n s i s scab ies setonii spec ies t anash iens i s tendae thioluteus vinaceus v i r idans vir idifaciens v i r id i s vi r idochromogenus wi l lmore i
chalcea spec ies
258
TABLE I I
Taxonomy to Spec ies
CLASS ORDER FAMILY GENUS SPECIES
Schizomycetes Eubacter ia les Achromobacter iaceae Achromobacter
Alcaligenes
Flavobacter ium
Azotobacter iaceae Azotobacter
Baci l laceae Bacil lus
Bac te r i aceae
Clostr idium
Bac te r ium
cyclocoastes (cycloclastes)
kashiwasakiensis liquidum spec ies
faecalis spec ies
androstenedionicum aquatile aurant iacum buccalis carbonii icum dehydrogenans f lavescens flavotennae fulvum helvoium m a r i s sewanense spec ies
agi l is chroococcum indicus oxydans spec ies vinlandii
alvei b rev i s c e r e u s c i rcu lans c los te ro ides coagulans coli fir mus lentus mac er an s me gâter ium mycoides poly my xa p ro teus pulvifaciens pumilus putr if icus pymilus r o s e u s spec ies sphaer icus subti l is thiaminolyt icus tumescens
bifermentans paraputr i f icum perf r ingens sporogenes t e r t i um welchii
bifidum cyclo -oxydans
TABLE I I
T a x o n o m y to S p e c i e s
259
CLASS
Schizomycetes
ORDER
Eubac te r ia les
FAMILY
Bac te r i aceae
Cor ynebacter iaceae
Ente robac te r iaceae
Lactobaci l laceae
Micrococcaceae
GENUS
Bac te r ium
Ar throbac te r
Cellulomonas
Corynebacter ium
Aerobacter
Erwinia
Escher ich ia
P ro t eus
Se r r a t i a
Catenabacter ium
Lactobaci l lus
Streptococcus
Micrococcus
Sarcina
SPECIES
havaniensis mycoides spec ies s te ro id ic las ium
s implex spec ies
biazotea
equi fascians helvolum hoagii mediolanum pseudodiphtheri t icum simplex spec ies xe rose
aerogenes cloacae
a ro ideae caro tovora
coli freundii
spec ies vulgar is
m a r c e s c e n s plymuthica
catenaforme spec ies
b rev i s buchneri bulgar icus
pyogenes
candidus c i t reus congloneratus dehydrogenans flava flavus luteus lysodeikt ius pi l tonensis pyogenus-aureus r o s e u s spec ies subflavus u reae va r i ans
a lbida albiden
260
TABLE I I
T a x o n o m y to S p e c i e s
CLASS
Schizomycetes
ORDER
Eubacter ia les
Pseudomonadales
FAMILY
Micrococcaceae
Rhizobiaceae
Methanomonadaceae
Pseudomonadaceae
GENUS
Sarcina
Staphylococcus
Agrobacter ium
Chromobacter ium
Rhizobium
Hydrogenomonas
Acetobacter
Azotomonas
Mycoplana
Phytomonas
Pro taminobac te r
Pseudomonas
SPECIES 1
aurent iace marginata var iabi l i s
albus aureus
ethanicus radiobacter tumefaciens
violaceum
leguminosarum me li loti phaseol i tr ifoli i
facilis
acet i pas teur ianum suboxydans xylinum
f luorescens
bullata dimorpha
c i t r i e icobatryae malvacearum
albofiavum r u b r u m
aeruginosa aureofaciens azoformicans boreopolis caudata chlor or aphis cohaerens cruciviae dacunhae desmolyt ica f luorescens fragi gaeger i gelidicola graveolens indoloxidans iner t ia j aeger i lacunogenes melanogenes myxogenes n i t roreductans ochracea oleovorans ovalis
TABLE I I
Taxonomy to Species
261
CLASS
Schizomycetes
OTHER TAXONOMIC GROUPS
Algae - Chlor op hy ta
P lan ts -
Spermatophyta Angiosperme Monocotyledonae
Dicotyledonae
Pro tozoa -
Mastigophora
Subclass :
Phytomast igina
Subclass :
Zoomastigina
ORDER
Pseudomonadales
Chlorococcales
Lil i i f lorae
Rosa les
Euglenoidina
Polymast igina
FAMILY
Pseudomonadaceae
Spir i l laceae
Chlorel laceae
Scenedesmaceae
Li l iaceae
Leguminosae
Euglenidae
Trichomonadidae
GENUS
Pseudomonas (continued)
Xanthomonas
Vibrio
Chlorel la
Scenedesmus
Sansevier ia
Medicago
Euglena
Tr ichomonas
Penta t r ichomonas
SPECIES
pavonacea pe r lu r ida p ic torum putida pyocyanea ra thonis riboflavinus r o s e u m schuylkill schuylki l l iensis spec ies s t r ia fac iens s tu tze r i synxantha t ae t ro lens t e s tos te ron i tr ifoli xanthe
c i t r i malvacerum
cyclosi tes metschnikovu perco lans tyrogenes
spec ies
spec ies
zeylanica
s at i va
g rac i l i s
foetus gallinae vaginalis
gal l inarum hominis
CHAPTER V
THE CONSTRUCTION AND USE OF TABLE I I I - TRANSFORMATIONS BY GENUS
ORDER OF THE TABLE
The entries in Table III include all the genera, species, sources, substrates, and reactions reported in the cited references. These include both inactive genera and assignments for reactions based solely on Chromatographie evidence.
Transformations that are documented with specific experimental details are cross-indexed with the product table. The references for those entries are under-lined.
The table entries are recorded in an order determined by the following rules which are applied sequentially.
(a) According to genus (alphabetically) (b) According to species (alphabetically) (c) According to source (alphabetically) (d) According to substrate (using the following systematic stem names
sequentially): estrane androstane pregnane cardanolide bufanolide cholanic acid cholestane stigmas tane sapogenins (common stem name)
Taxonomic names and identifying culture collection numbers, as well as the spellings of the genera, species, and varieties are as given in the cited references. Occasional changes in spelling were made to conform to standard reference texts or culture collection catalogs. In a few instances, to avoid misinterpretation, the prob-able correct spelling is given parenthetically.
SPECIFIC NOTES ON DIVISIONS OF THE TABLE
Genera The taxonomic position by class and order are given for each genus the first
time is appears in the table. A complete list of related families and genera can be found in Table II ("Taxonomy to Species"). Where more than one genus is tabulated on a page, the genus, in capital letters is repeated in the species column and under-lined.
262
SPECIFIC NOTES 263
Species An asterisk indicates that the corresponding entry in Table I ("Transformation
by Product") is recorded by the generic description (e.g. Aspergillus sp. for a list of species which perform the same transformation on a given substrate).
Occasionally, to better identify a species lacking a culture collection number, additional data are supplied, e .g. , Absidia orchidis (Vuill. ) hagem.
Transformations performed with one or more cultures (mixed or sequential) are recorded at the end of the list of substrates for the given species. Only the r e -action carried out by the primary culture is cited in the reaction column.
Transformations carried out by the second or third culture of the mixed group are listed parenthetically in the species column giving the full name of the culture and the particular reaction. The original references should be consulted for the experimental details.
When an organism has simply been identified as species in early work, but fully characterized in later reports, the final assignment is used giving the appropriate reference for the change. For example, Streptomyces argenteolus [Species ATCC-11009 (F-265, H-380, P-716, P-719; identified as argenteolus in F-267) ] .
Sources The source, with rare exceptions, is not related to the source from which the
culture was originally isolated but, wherever possible, to the major culture collec-tion where it can be obtained. The sources are coded and listed alphabetically (in-cluding the addresses) at the end of this chapter.
If the culture is not provided with an identifying number, the source is listed as either the name of the laboratory where the work was done or NG (not given).
All accession or identifying numbers for strains of a species are listed in numerical sequence. All identifying numbers for strains other than those available from the American Type Culture Collection or from the United States Department of Agriculture are enclosed in parentheses.
Different sources for the same species are listed alphabetically.
Substrates Systematic organic chemical nomenclature has been used, in most entries,
excepting for sapogenins and steroidal alkaloids. No more than one class of suffix designation for substituents is affixed to any stem. All remaining substituents are expressed in prefixes, arranged alphabetically.
In general, following the systematic stem name, the order of precedence, once the degree of substitution is established, is as follows.
(a) ane, ene, diene, triene (b) ol, diol, triol (c) one, dione, trione
For example, 5o?-pregnane-3,20-dione 3/3-hydroxy-5-pregnen- 20-one 4-pregnene-3,20-dione 6/3-hydroxy-4-pregnene-3,20-dione 17Œ, 2 l-dihydroxy-4-pregnene-3,20-dione 9a?-fluoro-17û?, 2l-dihydroxy-4-pregnene-3,20-dione 11/3,17a, 21-trihydroxy-4-pregnene-3,20-dione
264 V. CONSTRUCTION AND USE OF TABLE III
4-pregnene-3,11,20- trione 3j3-hydroxy-5,16-pregnadien-20-one
For Uie definition of terms such as nor, homo, and other notations with regard to nomenclature, see the explanations in the section on nomenclature in Chapter III.
Reactions The shorthand notation used to describe the reaction is identical with the nota-
tion used in Table I (cf. Chapter III). Reactions accomplished with cellfree enzymes and enzyme systems or those concerned with special effects of nutrients or environ-mental conditions are carried as notes in the substrate column under the appropriate culture.
A dash (—) in the reaction column indicates generally that no reaction took place or that the reaction was not characterized. Positive, though otherwise unspec-ified reactions are recorded as "oxidation - products not identified" or equivalent nonspecific terminology.
Two categories of entries are recorded in Table III (a) Those for which the ref-erence is underlined correspond to equivalent entries in Table I "Transformation by Product." To determine the structure of the product, thereby gaining access to Table I, the following rules apply. Rule 1: For those entries wherein no more than one hydroxylation appears in the
reaction column, the product is determined by the sum of all the recorded changes applied to the substrate.
Rule 2: For those entries wherein more than one hydroxylation is recorded, each hydroxylation determines a separate transformation product from the given substrate. Exception: A polyhydroxylation expressed as di-OH is read as a single, combined transformation of the substrate.
Examples: Substrate 3/3-hydroxy-5-pregnene-20-one
Reactions 3/3-OH — 3-C=0; Δ5-— Δ4 ; 12/3-OH i
Product 12/3-hydroxy-4-pregnene-3,20-dione
Substrate 3/3-hydroxy-5-pregnen-20-one +
Reactions 3/3-OH-— 3-C=0; Δ5-—Δ4 ; 12/3,15a-diOH
Product 12/3, 15a-dihydroxy-4-pregnene-3, 20-dione
Substrate 4-pregnene-3,20-dione +
Reactions 6/3-OH; l la-OH; 15/3-OH
Products 6/3-hydroxy-4-pregnene-3,20-dione 1 la-hydroxy-4-pregnene-3, 20-dione 15/3-hydroxy-4-pregnene-3,20-dione
Substrate 4-pregnene-3,20-dione +
Reactions 6/3-OH; l la-OH; 6/3, l la-diOH
Products 6/3-hydroxy-4-pregnene-3,20-dione lla-hydroxy-4-pregnene-3, 20-dione 6/3, lla-dihydroxy-4-pregnene-3,20-dione
SPECIFIC NOTES 265
(b) Entries which do not bear underlined reference citations have no equivalents in Table I. The reactions for these entries merely record the variety of transformations which may occur with the indicated substrate. For those instances in which multiple transformations are recorded, these may occur either in concert (to give a single product) or individually (and in combinations) to give multiple products.
References
The references for each entry are given by coded citation in the reference column. These citations are arranged alphabetically in the Bibliography (Chapter VI).
Those transformations for which there are data listed in Table I are identified by underlined references.
SOURCE OF CULTURES
Code Used to Identify Source in Transformation by Genus (Table III)
Code Source
Depar tment of Biochemist ry , R e s e a r c h Division, Abbott Labora to r i e s , North Chicago, 111.
Amer ican Cyanamid Co. (see a lso under LED), Lede r l e Division, P e a r l River , N. Y.
Armour and Co . , Chicago, 111.
Akimov State R e s e a r c h Insti tute (see under IPB)
Amer ican Type Culture Collection, 12301 Parklawn Drive, Rockeville, Md.
Ay e r s t R e s e a r c h Labora to r i e s , Montreal , Canada
Ben May Labora tory for Cancer Resea rch , Universi ty of Chicago, Chicago, 111.
Ciba Pharmaceu t i ca l P roduc t s , I n c . , Summit, N. J . and Basle , Switzerland
Centraa lbureau Voor Schimmelcul tures , Baarn, Nether lands
Microbiological Insti tute of Char les Univ. , Czechoslovakia
Commonwealth Mycological Inst i tute, Kew, Surrey , England
Depar tment of Plant Pathology, Cornel l Universi ty , Ithaca, N. Y.
Czechoslovak Academy of Agr icu l tura l Sciences, P rague , Czechoslovakia
Asterisk indicates major collections.
CZAS
EM
FAHU
FAKU
FARMIT
Czechoslovak Academy of Sciences, P rague , Czechoslovakia
E. Merck A. G. , Darmstad t , West Germany
Faculty of Agr icu l ture , Hokkaido Universi ty , Sapporo, Japan
Faculty of Agr icul ture , Kyushu Universi ty, Fukuoka, Japan
R e s e a r c h Labora to r i e s , Fa rmi ta l i a , Milan, Italy
AL
AMCY
ARMOUR
ASRI
ATCC*
AY
BEN MAY LAB
C
CBS*
CHARLES
CMI*
CORNELL
CZAA
266 V. CONSTRUCTION AND USE OF TABLE III
Code Source
Depar tment of Fermenta t ion Chemis t ry , Universi ty of Technical Science, P rague , Czechoslovakia
Fermenta t ion Resea rch Inst i tute, Agency of Indust r ia l Science and Technology, Japan
Hoechst A. G. , Frankfurt , West Germany
Insti tute of Applied Microbiology, Universi ty of Tokyo, Japan
Insti tute for Fermentat ion, 4-54, Juso-Nishinocho, Higashiyodogawa-Ku, Osaka, Japan Institut für Microbiologie und Exper imente l le Therap ie , Jena , W. Germany
R e s e a r c h Insti tute for Pha rmacy and Biochemis t ry , Kour imska 17, P rague , Czechoslovakia
Labora tory of Food Science, Kyoto Universi ty , Japan
Kagawa Universi ty, Japan
Depar tment of Botany, Kansas State College, Manhattan, Kans.
Leder le Labora to r i e s Division, Amer ican Cyanamid C o . , P e a r l River , N. Y. (see AMCY)
Leo Pharmaceu t i ca l Produc ts , Copenhagen, Denmark
R e s e a r c h Labora to r i e s , Lepetit , S . p . A . , Milan, Italy
Lilly R e s e a r c h Labora to r i e s , El i Lilly and C o . , Indianapolis, Ind.
Merck Culture Collection, Merck and C o . , Rahway, N. J .
Nagas Labora to r i e s , 380 Mi-Shuka-Cho, Setagayaku, Tokyo, Japan
National Agr icul tura l R e s e a r c h Inst i tute, Japan
National Collection of Indust r ia l Bac te r ia , Chemical R e s e a r c h Labora tory , Teddington, Middlesex, England
National Collection of Type Cul tures , Centra l Public Health Labora tory , London N .W. 9, England
Source not given
Nagao Insti tute, Tokyo, Japan
National Inst i tutes of Health, Bethesda, Md.
National Inst i tute of Health, Japan Nor thern Regional R e s e a r c h Labora to r i e s , Nor thern Utilization Branch, Agr icul tura l R e s e a r c h Service, U . S . Depar tment of Agr icul ture , Peor ia , 111.
Ohara Insti tute for Agr icul tura l Biology, Kurashiki , Japan
Depar tment of Biochemis t ry , Okayama Medical School, Okayama, Japan
R e s e a r c h Labora to r i e s , N. V. Organon, Nether lands
R e s e a r c h Labora to r i e s , Pa rk , Davis and C o . , Ann Arbor , Mich.
Char les Pf izer and Co . , New York, N. Y.
FCUTS
FRI
HOECHST
IAM
IFO
IMJ
IPB
K
KAG
KSC
LED
LEO
LEPETIT
LRL
MCC
NAGAS
NARI
NCIB*
NCTC*
NG
NI
NIH
NIHJ
NRRL*
OIAB OKAYAMA
OR
PD
P F
SPECIFIC NOTES 267
Source
N.V. Philips Duphar, Apollolaan 151, Amsterdam, Netherlands Research Institute for the Pharmaceutical Industry, Budapest, Hungary Quartermaster Culture Collection, Quartermaster Research and Engineering Command, United States Army, Natick, Mass. Research Institute of the Distillers and Preservation Industry, Prague, Czechoslovakia Research Institute for Natural Drugs, Prague, Czechoslovakia Department of Plant Pathology and Mycology, Rutgers University, New Brunswick, N. J . Sankyo Co., Ltd., Japan Schering A. G., Berlin, Germany Sandoz, Basle, Switzerland Research Laboratories, Schering Corporation, Bloomfield, N. J . G. D. Searle and Co., Chicago, 111. Shionogi Research Laboratory, Shionogi and Co., Ltd., Fukushima-Ku, Osaka, Japan School of Pharmacy, University of Wisconsin, Madison, Wise. Squibb Institute for Medical Research, E. R. Squibb and Son, New Brunswick, N . J . (Division of Olin Mathieson Chemical Corporation, New York, N. Y.) Soviet Union. Includes Institute of Microbiology of the Academy of Sciences of the USSR, Institute of the Chemistry of Natural Products of the Academy of Science of the USSR; S. Ordzhonikidze, All-Union Scientific Research Chemical - Pharmaceutical Institute Research Laboratories, Syntex, S. A., Mexico, D. F . Research Laboratories, Takeda Chemical Industries, Ltd., Juso-Nishino-Cho, Higashiyodogawa-Ku, Osaka, Japan Tokyo Biochemical Research Institute 2-593, Takadaminami-Cho, Toshima-Ku, Tokyo, Japan Tokai-Kinki National Agricultural Experiment Station, Japan Tsurumi Chemical Research Laboratories, Yokohama, Japan Institute of Organic Chemistry, University of Basle, Switzerland UpjohnCo., Kalamazoo, Mich. Department of Fermentation, University of Chemical Technology, Prague, Czechoslovakia University of Minnesota, Minneapolis, Minn. Research Laboratories, VEB Jena Pharm., Jena, Germany Waksman Collection, Institute of Microbiology, Rutgers University, New Brunswick, N. J .
Code
PH PIRI
QM*
RIDPI
RIND RUTGERS
S SAG SANDOZ SCH SEARLE SHIONOGI
S P-WISC SQ
SSSR
SY TAKEDA
TBRI
TNAES TSURUMI UB UC UCT
UM VEB WC*
268 V. CONSTRUCTION AND USE OF TABLE III
Ç2ËË Source
WFEB Worcester Foundation for Experimental Biology, Shrewsbury, Mass.
WISC Wisconsin Strain, University of Wisconsin, Madison, Wis.
WURB Western Utilization Research Branch, Agricultural Research Service, U. S. Department of Agriculture, Albany, Calif.
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus : ABSIDIA (Phyco. - Mucorales)
SPECIES
coerulea
cyl indrospora *
1 *
1 *
I glauca *
*
1 *
1 * 1 *
1 * 1 * 1 *
1 * 1 *
SOURCE
ATCC-1359b
RIDPI
NI
IPB
OIAB
UCT
SUBSTRATE
19-nor -4 -p regnene -3 ,20 -d ione
4 -p regnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione 21-ace ta te
4 -p regnene-3 ,20-d ione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
14j3-hydroxy-3-keto-5/3-20(22)-cardenolide
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide
4 -pregnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3 ,20-dione
17a, 21-dihydroxy-4-pregnene -3 ,20-dione 21-ace ta te
4 -p regnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
14/3-hydroxy-3-keto-5/3-20(22)-cardenolide
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide
4 -p regnene-3 ,20-d ione
REACTION
unidentified monohydr oxy la -tion
11a-OH; 11/3-OH
11a-OH; 11/3-OH; 1 1 - C = 0 (via 11/3-OH); 2 1 -OAc—21-OH
11a-OH; 14a-OH; 6/3,1 la -d iOH
6/3-OH;l la-OH
7/3-OH
3/3-OH-»3-C=0; lß-OH; 7/3-OH; 1/3,7/3-diOH; 5/3,7j3-diOH
l i a - O H
11/3-OH
6/3-OH;l la-OH
11/3-OH
1 1 - C = 0 (via 11/3-OH)
21-OAc^21-OH
11a-OH
14a-OH; 6/3, l l a - d i O H
11a-OH; 11/3-OH
6/3-OH
7/3-OH
3 /3 -OH-3-C=0 ; 1/3-OH; 5/3-OH; 7/3-OH
l/3,7/3-diOH;5/3, 7/3-diOH
l i a - O H
11/3-OH
R E F .
B-71
C-98
C-98
N-682
N-682
N-682
N-682
C-98
C-98
C-98
C-98
C-98
C-98
N-682
N-682
N-682
N-682
N-682
N-682
N-682
C-98
C-98
269
270
TABLE I I I
T r a n s f o r m a t i o n s by Genus: ABSIDIA
SPECIES
glauca
*
*
*
hyalospora *
*
*
orchidis (-)
orchidis
*
*
*
* *
*
SOURCE
UCT
VEB
NI
CZAA
NG
OIAB
pmi
SUBSTRATE
17a, 21 -dihydr oxy -4 -pr egnene -3,20-dione
17a, 21 -dihydroxy-4 -pr egnene -3,20-dione 21-aceta te
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
17a, 21 -dihydroxy-4-pr egnene -3,20-dione
14/3-hydroxy-3-keto-5/3-20(22)-cardenol ide
3/3,14/3-dihydroxy-5j3-20(22)-cardenolide
B -nor -4 -androstene -3 ,17 -dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
4-pregnene-3 ,20-d ione
17a, 21-dihydroxy-4-pr egnene -3 ,20-dione
14/3-hydroxy-3-keto-5/3-20(22)-cardenolide
4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
REACTION
6/3-OH; l l a - O H
11/3-OH
l l - C = 0 ( v i a 11/3-OH)
21 -OAc-21-OH
l l a - O H
11/3-OH
l l a - O H ; 14a-OH; 6/3,1 la-diOH
6/3-OH; l l a - O H ; 14a-OH
7ß-OH
3/3-OH— 3 - C = 0 ; 7/3-OH; 1/3,7/3-diOH; 5/3,7/3-diOH
6ξ-ΟΗ; l l a - O H
1/3-OH
l l a - O H
11/3-OH
1 1 - C = 0 (via 11/3-OH
l l a - O H
14a-OH; 6/3,11a-diOH
6/3-OH; l l a - O H
11/3-OH
3-C=0—3a-OH
5/3-H -> Δ4
l l a - O H
l l a - O H
11/3-OH
1 1 - C = 0 ( v i a 11/3-OH)
R E F .
C-98
C-98
C-98
C-98
C-98
C-98
N-682
N-682
N-682
N-682
P-741
S-825a
S-825a
S-825a
S-825a
N-682
N-682
N-682
C-98; H-334; N-682
N-682
N-682
C-98
C-98
C-98
271
TABLE I I I
T r a n s f o r m a t i o n s by Genus: ABSIDIA
SPECIES
orchidis
*
*
*
*
*
*
*
*
orchid is (Vuill. ) Hagem
*
SOURCE
PIRI
RDDPI
UCT (310)
VEB
OIAB
SUBSTRATE
17a ,21-d ihydroxy-4-pregnene-3,20-dione 21-ace ta te
17α, 21-d ihydroxy-4-pregnene-3,20-dione 21-ace ta te
4 -p regnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione 21 -aceta te
4 -p regnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3,20-dione 21-ace ta te
3/3,14/3-dihydroxy-5/3,17a-20(22)-cardenol ide
3/3, 14/3-dihydroxy-5/3-20(22)-cardenolide
REACTION
21-OAc^21-OH
l i a - O H
11/3-OH
1 1 - C = 0 (via 11/3-OH)
21-OAc->21-OH
l i a - O H
l i a - O H
1 1 - C = 0 ( v i a 11/3-OH)
21-OAC-21-OH
l i a - O H
l i a - O H
11/3-OH
1 1 - C = 0 (via 11/3-OH) 21-OAc-+21-OH
1/3-OH; 5/3-OH; 7ß-OH; 3/3-OH-» 3 - C = 0 ; 5/3-H-> Δ4
lß -OH
5/3-OH
7/3-OH
R E F .
C-98
C-98
C-98
C-98
C-98
C-98
C-98; H-334
C - 9 8 ; H-334
C-98
C-98
C-98
C-98
C-98
C-98
N-679; N-681
1-426; N-679; N-680; N-682; N-683; N-684
1-426; N-679; N-680; N-682; N-683; N-684
1-426; N-679; N-680; N-681 ; N-682; N-683; N-684
272
TABLE I I I
T r a n s f o r m a t i o n s by Genus: ABSIDIA
SPECIES
orchidis (Vuill. ) Hagem
r a m o s a
r egn ie r i
SOURCE
OIAB
NRRL
IAM
NG
SUBSTRATE
3/3,14/3-dihydroxy-5|3-20(22) -cardenolide
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
4-pregnene-3 ,20-d ione
17a-hydroxy-4-pregnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
11/3,21 -dihydroxy -4 -pregnene -3,20 -dione
17a, 21-dihydroxy-4-pr egnene-3,20-dione
4-pregnene-3 ,20-d ione
REACTION
1/3, 7/3-diOH
5/3,7/3-diOH
---
14a -OH
15/3-OH
6/3,14a-diOH
7/3,14a-diOH (revised s t ruc t -ure)
9a ,14a-diOH (assignment of s t ruc tu re -doubtful )
Π α - Ο Η
14α-OH
14α-OH
l l / 3 -OH-> l l -C=0
2/3-OH
11α-ΟΗ
14α-OH
6/3,14a-diOH
7/3,14a-diOH (revised s t r u c t -ure)
9a ,14a-diOH (assignment of s t ruc tu re -doubtful)
R E F .
1-426; N-679; N-680; N-682
1-426; N-679; N-682
M-587
M-587
M-587
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-120; S-859; T-982
S-844; S-859; T-982
S-844; T-982; T-1037
T-982
TABLE I I I
273
T r a n s f o r m a t i o n s by G e n u s : ABSIDIA
SPECIES
regn ie r i
repens
1 *
spec ies
SOURCE
NG
UCT
NG
SUBSTRATE
4-pregnene-3 ,20-d ione
17a-hydroxy-4-p regnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione ace ta te
11/3,21-dihydroxy-4-pregnene-3,20-dione
1 l a , 21 -dihydroxy -4 -pregnene -3,20-dione
21 -hyd roxy -4 -p regnene -3 ,11 ,20 -t r ione
17a, 21 -dihydroxy-4 -pregnene-3,20-dione
11/3,17a, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione ace ta te
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
Saponins (sapogenin glycosides)
REACTION
7/3,14a, 15/3-tri-OH (revised s t ruc ture )
l l a - O H
14a-OH
21-OAc-21-OH; 14a-OH
14a-OH
l l / 3 - O H - l l - C = 0
14a-OH;ll /3-OH
-n-c=o -
14a-OH
l l a - O H
14a-OH
-
l l a - O H ; 11/3-OH
l l a - O H ; 11/3-OH; 1 1 - C = 0 ( v i a 11/3-OH)
21-OAC-21-OH
l l a - O H
11/3-OH
R E F .
S-844; T-982; T-1037
S-859
S-841
S-841
S-841
S-851
S-841
S-841; S-851
S-851
S-841; S-851
S-841; S-844; S-859
S-841; S-844; S-859
S-851
C-98
C-98
C-98
C-98; N-682; S-801
C-98; S-801
K-478
274
T r a n s f o r m a t i o n s by Genus:
TABLE I I I
ACETOBACTER ACHROMOBACTER
TAXONOMY
(Schizo. - Pseudomonadales) (Schizo. - Eubacteriales)
SPECIES
acet i
(in mixed cul ture with Mycococcus sp. )
pas teur ianum
suboxydans
xylinum
(in mixed cul ture with Mycococcus sp. )
ACHROMOBACTER
cyclocoastes (cycloclastes)
kashiwasakiensis
liquidum
(in mixed cul ture with Mycococcus sp. )
SOURCE
IFO (3169)
NRRL
IFO ( A j
NG
NG
NRRL
IFOÎ3174)
NG
I F O ( A j
IAM
IAM
IFO (3084)
I F O ( A j
SUBSTRATE
l l / 3 ,17a ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
5-androstene-3/3,17/3-diol
5-androstene-3/3,17ß-diol 17-propionate
3/3-hydroxy-5-androsten-17-one
5-pregnene-3/3,17a,20/3,21-t e t r o l
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
5-cholesten-3/3-ol
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4-pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
11/3,17a, 21 - t r ihydroxy-4-p reg-nene-3 ,20-d ione
REACTION
-
—
-
-
3/3-OH— 3-C = 0 ; Δ 5 - Δ 4
3 | 3 -OH-3 -C=0 ; Δ -^Δ4
3 /3 -OH-3-C=0; Δ5 —Δ4
3 /3-OH^3-C=0; Δ 5 -Δ 4 ;20 /3 -ΟΗ - 2 0 - C = O
-
-
-
-
3/3-OH-*3-C=0; Δ 5 - Δ 4
-
11α-OH
6/3,14a-diOH
6/3-OH
-
Δ1
R E F .
1-428
M-587
M-587
M-587
1-428
K-457
K-457
K-457
L-523
M-587
M-587
M-587
1-428
K-457
1-428
S-849
T-1026
T-1026
1-428
1-428
275
T r a n s f o r m a t i o n s by Genus:
TABLE I I I ACREMONIUM ACROSPEIRA
ACROSTALAGMUS ACTINOMUCOR ACTINOMYCES
ACTINOP LANES
TAXONOMY
(Imperf. - Moniliales) (Imperf. - Moniliales) (Imperf. - Moniliales) (Phyco. - Mucorales) (Schizo. - Actinomycétales) (Schizo. - Actinomycetales)
SPECIES
species
ACREMONIUM
potronii
ACROSPEIRA
levis
ACROSTALAGMUS
albus
ACTINOMUCOR
corymbosus
repens
ACTINOMYCES
(See Streptomyces)
ACTINOPLANES
missour i ens i s
SOURCE
IAM (K-40-5)
FRI
NG
FRI
NG
NRRL
ATCC-14538
SUBSTRATE
4-pregnene-3 ,20-d ione
17a, 21 -dihydr oxy-4 -pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
not given
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
17/3- hydroxy- 17a -methyl -5a -andros tan-3-one
3/3-hydroxy-5-androsten-17-one
REACTION
6/3,14a-diOH
6/3-OH
—
17a-OH
6/3-OH; l l a - O H
-
-
-
-
1
Δ
3/3-OH— 3 - C = 0 ; Δ5 -» Δ4 ; Δ *
3 /3 -OH-3-C=0 · Δ5 — Δ4 ; Δ1
3/3-OH->3-C=0; /5 * 4 . A 1 .
Δ — Δ ; Δ ; 6/3-OH
R E F .
1-418
1-418
S-849
W-1106; W-1107
S-849
E-224
M-587
M-587
M-587
M-536
M-536; M-537
M-536; M-537
M-536; M-537
276
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by G e n u s : ACTINOPLANES AEROBACTER (Schizo. - Eubacter ia les)
SPECIES
missour i ens i s
(in sequential fermenta-tion with Curvular ia lunata [11/3-OH])
(in sequential fe rmenta-tion with Curvular ia lunata [11/3-OH])
spec ies
AEROBACTER
aerogenes
SOURCE
ATCC-14538
LRL-431
NCTC
NG
SUBSTRATE
l i a , 17/3-dihydroxy-4-androsten-3-one
17/3-hydroxy -17a - methyl -4 -andros ten-3-one
17/3-hydroxy-4-estren-3-one
4 -andros tene-3 ,17-d ione
4 -pregnene-3 ,20-d ione
4 -p regnene -3 ,11 ,20 - t r i one
21-hydroxy-4-pregnene-3 ,20-d ione
17a, 21 -d ihydroxy-4-pregnene-3 , 11 ,20- t r ione 21 aceta te
6a -f luoro-17a, 21 -dihydroxy-16a -methyl -4 -pregnene -3 ,20-dione
3j3-hydroxy-5-androsten-17-one
17/3-hydroxy-4-androsten-3-one
4 -androstene -3 ,17 -dione
5-cholesten-3/3-ol
5-cholesten-3/3-ol
3a ,7a ,12a- t r ihydroxy-5/3-cholanic acid
REACTION
Δ1; 17/3-OH — 17-C = 0
Δ1
enol.
Δ1
Δ1
1
Δ
Δ1
Δ1
Δ1; 21-OAc— 21-OH
Δ1
X
Δ
3/3-OH-3-C = 0 ; Δ 5 - Δ4; Δ1
3/3-OH-3-C = 0 ; Δ5 — Δ4 ; Δ *
3/3-OH->3-C=0;
6/3-OH
A1; 1 7 / 3 - O H -17-C = 0
1
Δ
-
—
—
R E F .
M-536
M-536
M-536
M-537
M-536
M-536
M-536
M-536
M-536
M-536
M-536
M-537
M-537
M-537
M-537
M-537
T-1030
S-914; W-1062
N-675
277
T r a n s f o r m a t i o n s by Genus :
TABLE I I I
AEROBACTER AGARICUS
AGROBACTERIUM
TAXONOMY
(Basidio. - Agar icales) (Schizo. - Eubacter ia les)
SPECIES
aerogenes (Izaki)
cloacae
AGARICUS
c a m p e s t r i s
eduiis
rodmani i
AGROBACTERIUM
ethanicus
(in mixed cul ture with Aspergi l lus wentii)
radiobacter
tumefaciens
SOURCE
ATCC-7256
ATCC-8308
ATCC-8329
ATCC-8724
IFO(3321)
IAM(l- l )
IAM(Al-2)
IAM (K-5)
FRI
NRRL-2334
AL(698)
WURB
NG
NRRL
IFO(3058)
SUBSTRATE
3a ,7a ,12a- t r ihydroxy-5 /3-cholanic acid
11/3,17a, 21- t r ihydr oxy -4 -p reg -nene-3 ,20-d ione
1 la, 21 -dihydr oxy -4 -pr egnene -3,20-dione
1 la, 21 -dihydroxy -4 -pregnene -3 ,20-dione
4 -p regnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
5-choles ten-3ß-ol
5-choiesten-3j3-ol aceta te
24j3-methyl-5 ,7 ,22-choies ta t r ien-3j3-ol
4 , 4 , 1 4 a - t r i m e t h y l - 5 a - 8 , 2 4 -cholestadien-3/3-ol
24-e thyl -5 ,22-choles tadien-3/3-ol
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
17a, 21-d ihydroxy-4-pregnene-3,20-dione
REACTION
-
-
-
-
-
-
-1
Δ
-
-
-
-
degradat ion
degradation
degradation
degradat ion
degradat ion
-
-
-
R E F .
S-849
S-849
S-849
S-849
1-428
1-428
1-428
S-849
S-849
R-778
S-825
R-778
T-1015; T-1016
T-1015; T-1016
T-1015; T-1016
T-1015; T-1016
T-1015; T-1016
M-587
M-587
M-587
S-849
278
T r a n s f o r m a t i o n s by G e n u s :
TABLE I I I
AGROBACTERIUM AGROCYBE
ALCALIGENES
TAXONOMY
(Basidio. - Agaricales) (Schizo. - Eubacteriales)
SPECIES
tumefaciens
(in mixed cul ture with Mycococcus sp. )
AGROCYBE
acer ico la
ALCALIGENES
faecalis
SOURCE
IFO(3058)
IFO
AL(SS-14)
IAM (ACC 101)
IAM (ACC 107)
NG
SUBSTRATE
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
1 la, 21 -dihydr oxy -4 -pr egnene - 3 , 20-dione
l ,3 ,5 (10) -es t ra t r i ene -3 ,17 /3 -d io l
1,3, 5 (10) -es t r a t r i ene -3 ,16a , 17j3-triol
3ß -hydroxy-5-androsten -17-one
3a, la ,12a - t r ihydroxy - 5/3 -cholanic acid
3a, 12a -dihydr oxy- 5/3 -cholanic acid
3a, 6a -dihydroxy - 5/3-cholanic acid
3a-hydroxy-5/3-cholanic acid
5-cholesten-3/3-01
REACTION
-
Δ1
-
-
—
-
-
keto der ivat ive
3 a - O H - 3 - C = 0
7a-OH—7-C=0
12a-OH-^12-C=0
3 a - O H - 3 - C = 0 ; 7 a - O H ^ 7 - C = 0
3a-OH->3-C=0; 12a-OH— 12-C = 0
7a-OH->7-C=0; 12a-OH-* 1 2 - C = 0
3 a - O H - 3 - C = 0 ; 7a-OH->7-C=0; 12a-OH->12-C=0
keto der ivat ive
keto der ivat ive
keto der ivat ive
degradation
R E F .
1-428
1-428
S-825
S-849
S-849
H-411
H-411
H-411
S-799
H-393; S-799
S-799
S-799
S-799
H-393; S-799
H-393; S-799; S-800
H-411
H-411
H-411
T-1030
279
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by G e n u s : ALLESCHERIA ALTERNARIA
(Asco. - Eurot ia les) ( Imperf. - Moniliales)
SPECIES SOURCE SUBSTRATE REACTION R E F .
species
ALLESCHERIA
Diodii
ALTERNARIA
bataticola
SCH (ON-1-42)
FRI
FAKU
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
1 la, 21 -dihydr oxy -4 -pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a,21-dihydroxy-5/3-pregnane-3,20-dione
4 -p regnene-3 ,20-d ione
1la -hydroxy-4 -p regnene -3 ,20 -dione
17a-hydroxy-4-p regnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
11/3,21-dihydroxy-4-pregnene-3,20-dione
Δ ; 20-C=O 20/3-OH
S-945
S-849
3-C = 0->3/3-OH
5j3-H
Δ -3-C:
Δ -3-C:
Δ 4 -3-C:
• 5/3-H; : 0 -3a
' 5/3-H; :Q->3/3
5/3-H
5/3-H; 0 ^ 3 a
Δ4 - - 5/3-H
Δ* -3-C
OH
OH
OH
OH
Δ -3-C:
Δ -3-C:
Δ -3-C:
> 5/3-H; = 0->3a
5/3-H
> 5/3-H; = 0 ^ 3 a - O H
' 5/3-H; = 0 — 3/3-OH
• 5/3-H
5ß-H; 0 - 3 a - O H
S-849
S-845
S-845; S-849; S-852
S-845; S-849; S-852
S-845; S-849; S-852
S-852
S-845
S-852
S-845; S-849
S-845; S-849; S-852
S-845; S-849; S-852
S-845; S-849; S-852
S-852
S-845; S-849; S-852
s
280
TABLE I I I
Transformations by Genus: ALTERNARIA
SPECIES
bataticola
c i t r i
kikutiana
pass i f lorae
SOURCE
S
FRI
TNAES
TNAES
NG
SUBSTRATE
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
170,21 -d ihydroxy-4-pregaene-3 ,11 ,20 - t r ione
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
1 la ,21-d ihydroxy-4-pregnene-3,20-dione
3/3-hydroxy-5-androsten-17-one
4 -andros tene-3 ,17-d ione
3/3-hydroxy-5-pregnen-20-one
3 ß , 21 -dihydroxy -5 -p re gnen- 20-one
4-pregnene-3 ,20-d ione
21-hydroxy-4-p regnene-3 ,20-dione
17a, 21-dihydroxy-4-pregnene-3,20-dione
1 l a , 2 1 -d ihydroxy-4-pregnene-3,20-dione
11/3, 21-dihydroxy-4-pregnene -3,20-dione
REACTION
Δ4 -> 5/3-H
Δ4 - 5j3-H; 3-C = 0 - 3 a - O H
Δ4 — 5ß-H; 3-C=0-*3/3-OH
Δ4 - 5/3-H
Δ4 - 5/3-H; 3 - C = 0 -3a -OH
Δ4 - ' 5/3-H
Δ4 - 5/3-H; 3 - C = 0 - 3 a - O H
-
-
-
Δ1
Δ1
Δ1
Δ1
Δ1
Δ
Δ1
Δ1
Δ1
R E F .
S-845; S-849; S-852
S-845; S-849; S-852
S-845; S-849; S-852
S-845; S-849; S-852
S-845; S-849; S-852
S-845; S-849; S-852
S-845; S-849; S-852
S-849
S-849
S-849
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
281
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: ALTERNARIA
AMANITA (Basidio. - Agaricales)
SPECIES
pass i f lorae
(in sequential fermentat ion with Curvular ia lunata [11/3], Ophiobolus herpotrichus[21-OHl and Leptosphaer ia maculans [17-OH])
AMANITA
mucar ia
porphyr ia
SOURCE
NG
CMI
NG
NRRL
AL(H-26) A L ( F - 6 )
AL(H-104)
SUBSTRATE
11α, 17α, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r i one
l l /3 ,21-d ihydroxy-3 ,20-d ike to-4 -p regnen-18-a l
11/3, 17a ,21 - t r i hyd roxy-3 ,20 -d ike to -4 -pregnen-18-a l
4 -p regnene-3 ,20-d ione
Hecogenin glycoside
4 -p regnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
l l ß , 21 -dihydroxy -4 -pregnene -3,20-dione
1 la, 21 -dihydroxy -4 -pregnene -3 ,20-dione
1 la, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r i one
3/3,6/3,8/3,14/3-tetrahydroxy-4, 20,22 -bufatrienolide 6-aceta te 3-glucoside
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
REACTION
Δ1
Δ1
Δ1
Δ1
1
Δ
3/3 - glycoside (saponin) —» 3/3-OH
Δ1; 17/3-Ac -> 17-C = 0
1
Δ
Δ1
Δ1
Δ1
^ - [ l ^ - g l u c o s i d e ] -» 3/3-OH
-
-
-
-
R E F .
W-1105
W-1105
W-1105
W-1105
W-1107
H-351
V-1053
V-1053
V-1053
V-1053
V-1053
S-936a
M-587
M-587
M-587
S-825
S-825
species
282
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by G e n u s : ARMILLARIA
ARTHROBACTER (See Corynebacter ium)
(Basidio. - Agaricaies) ;' Schizo. - Eubacter ia les)
SPECIES
ARMILLARIA
mellea
ARTHROBACTER
(See Corynebacter ium)
simplex
SOURCE
WURB (M-6a)
ATCC-6946
UV( mutant)
(enzyme prepara t ion)
SUBSTRATE
4-pregnene-3 ,20-d ione
17/3-hydroxy-4-estren-3-one
4-pregnene-3 ,2C-dione
5-pregnene-3/3 ,17a,21- t r io l -2C-one 3 ,21-diace ta te
1 la, 21 -dihydr oxy -4 -pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r ione
11/3,17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
3 ,20-d ioxo- l l /3 -hydroxy-4-preg-nen-18-oicacid(18 —»11) lactone
17/3-hydroxy-4-estren-3-one
5-pregnene-3/3,17a, 21 - t r i o l -20 -one 3 ,21-diace ta te
4 -andr ostene -3 ,17 -dione
REACTION
-
1
Δ ; enol.
1
Δ ; enol. ; 17/3-OH - 17-C = 0
1
Δ 1 5 4
Δ1; Δ - Δ ; 3/3-OH-+ 3-C = 0 ; 20-C = O-> 20/3-OH; 3 , 2 1 -diOAc — 3 , 2 1 -diOH; degradation
Δ1
Δ1
Δ - high concen t ra t ion , 50 gm subs t ra te pe r 100 ml broth
Δ1
Δ ; enol. ; 17/3-OH — 17-C = 0
A l A 5 A 4
Δ ; Δ —► Δ ; 3j3-OH—3-C=0; 3,21-diOAc — 3,21-diOH no degradation
Δ1
R E F .
R-778
K-463
C-116
K-463
C-115
K-463
K-463
K-463; K-467
U-1044
C-116
C-115
K-463
283
TABLE I I I
TAXONOMY
Transformat ions by Genus: ARTHROBACTER (See Corynebacterium)
ARTHROBOTRYS (Imperf. - Moniliales)
SPECIES
simplex
(Jensen) Lochhead
species
ARTHROBOTRYS
conoides
1 dactyloides
1 musiformis
1 superba var . ol igospora
SOURCE
ATCC-13260 (Searle B-22-8)
NG
NG
ATCC-14560
Sear le (20-178)
Sear le (B-20-27)
Sear le (B-22-9)
NG
NG
NG
NG
SUBSTRATE
4 -andros tene -3 ,17 -dione
19-hydroxy-4-andros tene-3 ,17 -dione
9a- f luoro- l l /3 ,16a , H a ^ l - t e t r a -h y d r o x y ^ - p r e g n e n e - S , 20-dione
6 a - f l u o r o - l l ß , 17a ,21- t r ihydroxy-16a -me thy l -4 -p regnene -3 ,20 -dione
6a-f luoro- l l /3 ,14α, 17α, 2 1 - t e t r a -hydroxy-16a-methy l -4 -p re g-nene-3 ,20-d ione
3/3-hydroxy-12a- a z a - C - h o m o -5a-pregnane-12 ,20-d ione aceta te
4 -andros tene -3 ,17 -dione
9a-hydr o x y - 4 - a n d r o s t e n e - 3 , 1 7 -dione
17a[21-carboxyethyl]-17i3-hydroxy-4-andros ten -3 -one lactone
9a -hyd roxy-4 -p regnene -3 ,20 -dione
9a-hydroxy-4-andros tene - 3 , 1 7 -dione
17a, 21-dihydr oxy-4-p regnene-3,20-dione
17a, 21-dihydr oxy-4-p regnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene 3,20-dione
REACTION
Δ1
9a-OH; Δ* r e v e r s e aldol
1
Δ ; r e v e r s e aldol (Formaldehyde \ ) enol.
1
Δ
Δ 1
1
Δ
3 ß - O A c -3-c=o; Δ1
1
Δ
Δ ; r e v e r s e aldol; enol.
Δ1
17/3-Ac— 1 7 - C = 0
Δ ; r e v e r s e aldol; enol.
-
-
-
6/3-OH
11a-OH
11/3-OH
R E F .
D-171; M-597
D-171; M-597
M-597
T-1007
U-1042
U-1042
M-563
D-170
D-170
C-121
D-172
D-172
E-226
E-226
E-226
E-226
E-226; E-227
E-226; E-227
284
TABLE I I I TAXONOMY
Transformat ions by Genus: ASCOCHYTA ASPERGILLUS
(Imperf. - S^haeropsidales) ylmperf. - Moniliales)
SPECIES
ASCOCHYTA
favae
linicola
pinadella
viciai
ASPERGILLUS
aculeatus
a l l iaceus
*
*
amste lodami
*
SOURCE
FAKU
NRRL-2923
FAKU
FRI
IAM
CZAA
IAM
CZAA
IAM
SUBSTRATE
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
17/3-hydroxy -4 -andr osten -3-one
17j3-hydroxy-l 7a- methyl -4 -andros ten-3-one
4 -pregnene-3 ,20-d ione
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
17a, 21 -dihydroxy-4 -pregnene -3,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione aceta te
1 Iß , 21 -dihydroxy-4 -pregnene-3,20-dione
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
4-pregnene-3 ,20-d ione
4 -andros tene-3 ,17-d ione
3/3-hydroxy-5-pregnen-20-one
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -andros tene-3 ,17-d ione
3/3-hydroxy- 5 -pregnen -20 -one
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
REACTION
-
9a-OH
9a-OH; 17/3-OH - 17-C = 0
9a-OH
9a-OH
9a-OH
9a-OH
9a-OH; 21-OAc - 21-OH
9a-OH
-
-
-
17-C = 0 -*17a -o x a - 1 7 - C - O
Δ5—Δ4; 3/3-OH - 3-C = 0
17j3-Ac-17a-oxa-17-C = 0
11a-OH
-
Δ 5 - Δ 4 ; 3/3-OH - 3 - C = 0
11a-OH; metabo l i t e -X
R E F .
S-849
S-828
S-828
S-828
S-828
S-828
S-828
S-828
S-828
S-849
S-849
1-416; 1-417
C-104
C-104
C-104
1-416; 1-417
C-104
C-104
C-104
1-416; 1-417
TABLE I I I
Transformat ions by Genus·. ASPERGILLUS
285
SPECIES
amste lodami *
a s p e r e s c e n s
as t ianus
a t ropurpureus
*
aureus *
I aur icomus
avenaceus
awamori (Nakazawa) *
awamori
| *
batatae
brevipes
butyracea
caes ie l lus
SOURCE
MCC
IAM
IAM
CZAA
IAM
IAM
IAM
NRRL (An-S)
CZAA
IAM (K-0625, K-0924, K-3532, K-5112)
NG
IAM
IAM
IAM
IAM
SUBSTRATE
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-andros tene-3 ,17-d ione
3/3-hydroxy-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
Saponins (sapogenin glycoside)
4 -andros tene-3 ,17-d ione
3/3-hydroxy-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
17a -hydroxy-4 -p regnene -3 ,20 -dione
1 la, 21 -dihydr oxy -4 -pregnene - 3 , 20-dione
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
REACTION
l l a - O H ; 6/3,11a-diOH
l l a - O H
6/3,1 la-diOH
metaboli te - X
Δ5 - Δ4; 3/3-OH - 3 - C = 0
metaboli te - X
Πα-ΟΗ; 6/3, Πα-d iOH
-
-
3/3-glycoside (saponin) —» 3/3-OH
-
Δ5—Δ ; 3/3-OH - 3 - C = 0
l l a - O H
l i a - O H
l i a - O H ; 6/3, l l a - d i O B
-
-
-
-
-
—
R E F .
D-190
1-416; 1-417
1-416
C-104
C-104
C-104
I 416; 1-417
1-416; 1-417
1-416; 1-417
K-478; K-479
C-104
C-104
C-104
1-416; 1-417
S-859
S-859
S-859
1-416; 1-417
1-416; 1-417
1-416; 1-417
1-416; 1-417
286
TABLE I I I
Transformat ions by Genus.· ASPERGILLUS
SPECIES
caespi tosus
* candidus
*
*
carbonar ius
carneus
*
cheval ier i
1 *
SOURCE
IAM
MCC
CZAA
FRI
IAM
MCC
SSSR (28)
IAM
MCC
CBS
IAM
CZAA
SUBSTRATE
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -andros tene-3 ,17-d ione
3/3-hydroxy-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene - 3 , 1 1 , 2 0 - t r i o n e
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
3 -hydroxy -1 ,3 ,5(10) - e s t r a t r i e n -17-one
l , 3 ,5 (10 ) -e s t r a t r i ene -3 ,17 j3 -d io l
4 -pregnene-3 ,20-d ione
4 -andros tene-3 ,17-d ione
3/3 -hydroxy -5 -pregnen-20 -one
REACTION
-
11a-OH
metaboli te - X
Δ 5 ^ Δ 4 ; 3/3-OH - 3 - C = 0
metabolite - X
-
11a-OH
11a-OH,
11a-OH; 6/3, l l a - d i O H
-
-
-
7a-OH
15a-OH
7a-OH; 1 7 - C = 0 - 17/3-OH
15a-OH; 1 7 - C = 0 — 17/3-OH
7a-OH
15a-OH
7a-OH; 17/3-OH — 1 7 - C = 0
15a-OH; 17/3-OH - 1 7 - C = 0
l l a - O H ; 6)3, l l a - d i O H
17-C=0—17a-o x a - 1 7 - C = 0
Δ 5 - Δ 4 ; 3j3-OH - > 3 - C = Q
R E F .
1-416; 1-417
D-190
C-104
C-104
C-104
S-849
1-416; 1-417
D-190
T-1010
T-1010
1-416; 1-417
D-190
L-495; L-497
L-495; L-497
L-495; L-497
L-495; L-497
L-495; L-497
L-495; L-497
L-495; L-497
L-495; L-497
1-416; 1-417
C-104
C-104
TABLE I I I
T ransformat ions by Genus: ASPERGILLUS
287
SPECIES
cheval ier i
*
*
cinnamomeus
*
*
ci t r i
c i t r i sporus *
clavatus
1 *
1 * conicus *
echinulatus *
1 * effusus
1 *
SOURCE
IAM
MCC
NG
NRRL (CZ-43)
CZAA
IAM
FRI
IAM
ATCC-9598
ATCC-10058
CZAA
IAM
MCC
MCC
IAM
MCC
CZAA
SUBSTRATE
4-pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
Saponins (sapogenin glycosides)
4 -andros tene -3 ,17 -dione
3/3-hydroxy-5-pregnen-20-one
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
4 -p regnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione ace ta te
4 -p regnene-3 ,20-d ione
4 -andros tene -3 ,17-d ione
3/3-hydroxy-5-pregnen-20-one
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -andros tene -3 ,17-d ione
3/3-hydroxy- 5 -pregnen -20 -one
REACTION
-
l i a -OH; 6/3, l la-diOH
17/3-Ac^ 17-C = 0
1 7 / 3 - A c ^ l 7 a -o x a - 1 7 - C = 0
3/3-glycoside (saponin) —» 3/3-OH
metaboli te - X
Δ 5 - * Δ 4 ; 3/3-OH->3-C=0
metaboli te - X
l i a - O H ; 6/3, l l a - d i O H
-
l i a - O H ; 6/3, l l a - d i O H
l i a - O H ; 2 1 -OAc - 21-OH
l i a - O H
-
Δ5->Δ4; 3/3-OH - 3 - C = 0
l i a - O H
l l a - O H ; 6/3, l l a - d i O H
l l a - O H
l l a - O H
l l a - O H ; 6/3, l l a - d i O H
l l a - O H
-
Δ 5 - Δ 4 ; 3/3-ΟΗ - 3 - C = 0
REF.
1-416; 1-417
D-190
C-102
C-102
K-478; K-479
C-104
C-104
C-104
1-416; 1-417
S-849
1-416; 1-417
M-603
M-603
C-104
C-104
C-104
1-416; 1-417
D-190
D-190
1-416; 1-417
D-190
C-104
C-104
288
TABLE I I I
Transformat ions by Genus: ASPERGILLUS
SPECIES
ei iusus
elegans
*
f ischeri
*
flavipes
*
*
*
SOURCE
CZAA
CZAA
IAM
ATCC-1G20
CZAA
IAM
MCC
ATCC-11013
CZAA
IAM
MCC
SUBSTRATE
4-pregnene-3 ,20-d ione
4 -andros tene-3 ,17-d ione
3/3-hydroxy-5-pregnen-2G-one
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
21-hydroxy-4-p regnene-3 ,20-dione aceta te
4 -andros tene-3 ,17-d ione
3/3 -hydroxy- 5 -pregnen -20 -one
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -andros tene-3 ,17-d ione
17a-oxa-D-homo-4-andros tene-3,17-dione
4 -pregnene-3 ,20-d ione
4 -andr ostene -3 ,17 -dione
3/3-hydroxy -5 -pregnene -20 -one
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
REACTION
l l a - O H
metabolite - X
Δ 5 - Δ 4 ; 3β-ΟΗ - 3 - C = 0
metabolite - X
l l ö - O H ; 6,3, l l a - d i O H
21-OAc—21-OH; l l a - O H
17-C = 0 -> 17a-oxa-17-C = 0
no oxidation at 3-C
17j3-Ac-»17a-oxa-17-C = 0
l l o - O H ; 6/3, l l a - d i O H
11a-OH
17-C = 0 - 1 3 , 1 7 -seco-13a-OH-16-COOH
17a-oxa-17-C = 0 — 13 ,17 - seco -13ö-OH-16-COOH
17|3-Ac->17a-oxa-17-C = 0
17/3-Ac—13,17-seco-13a-OH-16-COOH
17-C = 0 - 17a-oxa-17-C = 0
Δ 5 - Δ 4 ; 3/3-OH -> 3-C = 0
17/3-Ac-» 17a -oxa-17-C = 0
l l a - O H ; 6/3, l l ö -d iOH
l l a - O H ; 6/3, l l a - d i O H
R E F .
C-104
C-104
C-104
C-104
1-416; 1-417
M-603
C-104
C-104
C-104
1-416; 1-417
D-190
H-398
H-398
F-270
H-398
C-104
C-104
C-104
1-416; 1-417
D-190
TABLE I I I
Transformations by Genus: ASPERGILLUS
289
SPECIES
fia vu s
*
*
*
1 *
SOURCE
ATCC-9170
ATCC-9807
CZAA
FRI
IAM
IPB
MCC
NG
NRRL
SUBSTRATE
4-pregnene-3 ,20-d ione
Saponins (sapogenin glycosides)
4 -andros tene -3 ,17-d ione
3j3-hydroxy-5-pregnen-20-one
4 -p regnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
5-androstene-3/3,17a-diol
5-androstene-3/3,17/3-diol
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
17a -hydroxy-4 -p regnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
1 la, 21 -dihydroxy -4 -pregnene -3 ,20-dione
Sarsasapogenin
Diosgenin
REACTION
l i a - O H
hydrolysis of glycosides to aglycones (sapogenins)
17 -C=0—17a-o x a - 1 7 - C = 0
Δ5-*Δ4; 3/3-ΟΗ ^ 3 - C = 0
17/3-Ac—17a-o x a - 1 7 - C = 0
-
l i a - O H ; 6/3, l l a - d i O H
3 /3 -OH-3-C=0; A 5 A 4
Δ —>Δ
3 /3 -OH-3-C=0; Δ 5 ^ Δ 4
l i a - O H
17/3-Ac -> 1 7 - C = 0
17j3-Ac-»17a-o x a - 1 7 - C = 0
17a-OH-17/3-Ac —>17a-oxa-17-C = 0
17j3-(20-C=O-21-OH)-» 1 7 - C = 0
17/3-(20-C = O-2 1 - O H ) - 1 7 a -o x a - 1 7 - C = 0
17a-OH-17/3-(20 -C=O-21 -OH)->17-C = 0
17a-OH-17/3-(20 -C=O-21-OH)-+17a-oxa-1 7 - C = 0
-
-
R E F .
M-603
K-478
C-104
C-104
C-104 1
S-849
1-416; 1-417
H-337
H-337
D-190
P-726
P-726
P-726
P-726
P-726
P-726
P-726
M-587
M-587
290
TABLE I I I
T r a n s f o r m a t i o n s by Genus : ASPERGILLUS
SPECIES
f lavus
*
fonsecaeus
fu mi gat us
*
*
*
*
*
fumigatus F r e s .
giganteus
*
glaucus
*
SOURCE
NRRL
SSSR (27)
IAM
CZAA
IAM
IAM
MCC
NRRL
SSSR (12)
SSSR (14)
NG
ATCC-1005a
IAM
IAM (mutant)
IAM
NRRL (CZ-5)
SSSR
SUBSTRATE
4 -dehydrotigogenone
4-pregnene-3,2G-dione
4 -p r egnene -3 ,11 ,20 - tr ione
4-pregnene-3 ,20-d ione
4 -andros tene-3 ,17-d ione
3/3-hydroxy-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
21-hydroxy-4 -p regnene-3 ,20-dione
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -pregnene -3 ,11 ,20 - t r i one
3/3,6j3,8/3,14-tetrahydroxy-4, 20,22 -bufatrienolide 6-aceta te 3-glucoside
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
Saponins (sapogenin glycosides)
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r ione
REACTION
—
6/3,1 la-diOH
-
-
metabolite - X
Δ5 - Δ 4 ; 3/3-OH -» 3 - C = 0
metabolite - X
l l a - O H ; 6/3, l l a - d i O H
-
11a-OH
11/3-OH
-
-
-
6/3, l la-diOH
6/3,1 la -diOH
-
3/3-fl^-glucosidel — 3/3-OH
lla,15/3-diOH
11a-OH; 6/3, l l a - d i O H
-
—
3/3-glycoside (saponin) —» 3/3-OH
—
R E F .
M-587
T-1010
T-1010
1-416; 1-417
C-104
C-104
C-104
1-416; 1-417
1-416; 1-417
D-190
H-328
M-587
M-587
M-587
T-ioio
T-1010
T-1010
S-936a
D-179; D-180
1-416; 1-417
D-190
1-416; 1-417
K-478; K-479
T-1010
(mutant)
TABLE I I I
T rans format ions by Genus: ASPERGILLUS
291
SPECIES
grac i l i s *
gymnosardae
he rba r io rum
inuii *
i taconicus
janus
japonicus *
kanagaw-aensis
kawachii
luchuensis
1 *
1 * mangini *
1 mel leus
1 *
I minimus * (minutus)
miyakoensis *
SOURCE
IAM
MCC
IAM
IAM
IAM
ATCC-10021
IAM
IAM
IAM
IAM
IAM
ATCC-10061
CZAA
MCC
MCC
CZAA
IAM
IAM
IAM
SUBSTRATE
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene -3 ,2 0-dione
4-pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -andros tene -3 ,17-d ione
3/3-hydroxy-5-pregnen-20-one
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -andros tene-3 ,17-d ione
3/3-hydroxy-5-pregnen-20-one
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,2 0-dione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
REACTION
l l a - O H ; 6/3, l l a - d i O H
-
-
-
l i a - O H 5 6/3, l l a - d i O H
l l a - O H
l i a - O H ; 6/3, l l a -d iOH
-
l l a - O H ; 6/3, l l a - d i O H
-
-
l l a - O H
-
Δ5->Δ4; 3j3-OH-> 3 - C = 0
l l a - O H
l l a - O H
l l a - O H
-
Δ5->Δ4; 3/3-OH —3-C=0
l l a - O H
-
l l a - O H ; 6/3, l l a - d i O H
l l a - O H ; 6/3, l l a - d i O H
R E F .
1-416; 1-417
D-190
1-416; 1-417
1-416; 1-417
1-416; 1-417
M-603
1-416; 1-417
1-416; 1-417
1-416; 1-417
1-416; 1-417
1-416; 1-417
M-603
C-104
C-104
C-104
D-190
D-190
C-104
C-104
C-104
1-416; 1-417
1-416; 1-417
1-416; 1-417
292
TABLE I I I
Transformat ions by Genus: ASPERGILLUS
SPECIES
mollis *
montevidensis *
nakazawai *
nidulans
*
*
*
SOURCE
IAM
MCC
IAM (K-2C24)
ATCC-10C74
ATCC-11267
CZAA
IAM
MCC
NRRL
SUBSTRATE
4-pregnene-3 ,20-d ione
4-pregnene-3,2C-dione
4 -p regnene-3 ,2" -d ione
4 -p regnene -3 , 2·! -dione
I6a-hydroxy -4 -pregnene - 3 , 2.° -dione
21-hydroxy-4-p regnene-3 ,20-dione acetate
1 7ÛÎ , 21 -dihydroxy -4 -pregnene -3, 20-dione
4 , 9 ( l l ) - p r e g n a d i e n e - 3 , 20-dione
A-nor -3 -p regnene -2 ,20 -d ione
6a - fluor o -1 la - hydroxy - 4 -p regnene-3 ,20-d ione
6a - chlor o -17a - hydroxy - 4 -p regnene-3 ,20-d ione
6a - chlor o -17a, 21 -dihydroxy-4 -pregnene-3 ,20-d ione
6a -fluoro -17a, 21 -dihydr oxy - 4 -p regnene-3 ,20-d ione
4 -andros tene-3 ,17-d ione
3/3-hydroxy-5-pregnen-20-one
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
REACTION
l i a - O H ; 6/3, I l a -d iCH
l i a - O H
Ha-OK; 6/3, l l a -d iOH
l i a - O H
6/3 -OH
l i a - O H ; 2 1 -OAc —21-OH
l l a - O H
6/3,12a-diOH
6/3-OH
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
15ß-OH
-
Δ5—Δ4; 3/3-ΟΗ-* 3-C = 0
l l a - O H
l l a - O H ; 6/3, l l a -d iOH
l l a - O H
-
—
R E F .
1-416; 1-417
D-19C-
1-416; 1-417
M - O C J
F-265; F-257; F-288
M-603
F-288
F-277; F-279
T-1006; W-1076
T-1006; W-1076
F-268
F-268
F-268
F-268
F-268
C-104
C-104
C-104
1-416; 1-417
D-190
M-587
M-587
M-587
TABLE I I I
T r a n s f o r m a t i o n s by Genus : ASPERGILLUS
293
SPECIES
nidulans
*
* niger
SOURCE
SSSR
SSSR (13)
SSSR (23)
ATCC-6257
ATCC-9142
ATCC-9145
SUBSTRATE
1 l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
4 -p regnene-3 ,20-d ione
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
4 -p regnene-3 ,20-d ione
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
4 -p regnene-3 ,20-d ione
A-no r -3 -p regnene -2 ,20 -d ione
19 -nor -4 -p regnene -3 ,20 -d ione
4 -p regnene-3 ,20-d ione
6/3-hydroxy-4-pregnene-3 ,20-dione
1 l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
11/3-hydroxy-4-pregnene-3,20-dione
14a -hydroxy-4 -p regnene -3 ,20 -dione
17a -hydroxy-4 -p regnene -3 ,20 -dione
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
1 9 - n o r - 4 -pregnene -3 ,20-d ione
3/3-hydroxy - 5-pregnen-20-one
4 -p regnene-3 ,20-d ione
6/3-hydroxy-4-pregnene-3, 20-dione
11/3-hydroxy-4-pregnene-3, 20-dione
17a -hydroxy-4 -p regnene -3 ,20 -dione
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
REACTION
-
l l a - O H ; 6/3, l l a - d i O H
17a-OH
l l a - O H ; 6/3, l l a - d i O H
17a-OH
l i a - O H
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
R E F .
T-1010
T-1010
T-1010
T-1010
T-1010
M-603
W-1077
Z-1123; Z-1124
Z-1123; Z-1124
Z-1123; Z-1124
Z-1123; Z-1124
Z-1123; Z-1124
Z-1123
Z-1124
Z-1123; Z-1124
R-783
R-783
R-783
R-783
R-783
R-783
R-783
294
TABLE I I I
Transformat ions by Genus: ASPERGILLUS
SPECIES
niger
*
*
*
SOURCE
ATCC-10549
ATCC-10577
CZAA
FRI
IAM
MCC
NG
SUBSTRATE
4-pregnene-3 ,20-d ione
5/3 -pr egnane -3 ,20 -dione
4 -pregnene-3 ,20-d ione
17a-hydroxy-4-p regnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
4 ,16 -pregnadiene -3 ,20-dione
4 -andros tene -3 ,17 -dione
3ß-hydroxy-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -andros tene-3 ,17-d ione
A-nor -3 -p regnene -2 ,20 -d ione
d , l -3 /3-hydroxy-5-pregnen-20-one
3)3-hydroxy-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
16a-hydroxy-4-p regnene-3 ,20-dione
(20S)- 20-hydr oxy-18,20-cyclo- 4-pregnen-3-one
REACTION
l i a - O H
l i a - O H
l i a - O H
l i a - O H
l i a - O H
l i a - O H
l i a - O H ; Δ1 6-17-Ac—► 17a-Ac
-
3/3-OH->3-C=0; Δ 5 - Δ 4
l i a - O H
-
l l a - O H ; 6j3, l l a - d i O H
l l a - O H ; 6j3, l l a - d i O H
6/3-OH
21-OH
d,I-3/3-OH-+ d - 3 - C = 0 + 1-3/3-OH
3 / 3 - O H - 3 - C = 0 ; Δ 5 - Δ 4
3 j 3 - O H - 3 - C = 0 ; Δ5->Δ4; l l a - O H
3|3-OH-^3-C=0; Δ 5 - Δ 4 ; 6j3, l l a - d i O H
l l a - O H
l l a - O H
-
R E F .
M-603
M-603
M-603
M-603
M-603
M-603
M-603
C-104
C-104
C-104
S-849
1-416; 1-417
D-190
F-288
L-502
W-1102
P-710
F-288
F-288
M-566
F-265; F-267; F-283
W-1071
TABLE I I I
T ransformat ions by Genus: ASPERGILLUS
295
SPECIES
niger
*
1 *
I niveo-glaucus *
1 niveus *
SOURCE
Sandoz NG
NRRL-3 ,328 , 330,334,1292
ALCA(5 TC-251-4247)
PIRI(47)
PIRI (mutant)
SSSR(3, 10, 25)
SSSR121, 2 2 , 2 4 , 2 9 , 30,31,33)
SSSR(2, 7 ,10 ,29 ,31)
SSSR(3, 4 , 5 , 6 , 8 , 2 1 , 2 2 , 2 4 , 2 5 , 3 0 , 33)
WISC(72-2)
MCC
MCC
SUBSTRATE
3ß, 6/3,8/3,14/3-tetrahydroxy-4, 20,22 -bufatrienolide 6-aceta te 3-glucoside
Saponins (agave)
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -pregnene - 3 , 1 1 , 2 0 - t r ione
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
4 -p regnene-3 ,20-d ione
17a -hydroxy-4 -p regnene -3 ,20 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
6a-f luoro-17a, 21-d ihydroxy-4-p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
REACTION
3/3-[ lVghicoside] — 3/3-OH
3/3-glycoside (saponin) —* 3/3-OH
l i a - O H
l l a , 2 1 - d i O H
l i a - O H (only)
l i a - O H
l i a - O H ; 6/3, l l a - d i O H
17a-OH
l i a - O H
6/3,1 la -d iOH
l l a - O H
l i a - O H ; 17a-OH-17/3-Ac -» D - h o m o - 1 7 a | -OH-17a£-Me-1 7 - C = 0
l l a - O H
l l a - O H
l l a - O H
l l a - O H ; 6/3, l l a - d i O H
l l a - O H
R E F .
S-936a
K-479
W-1120
W-1081; W-1120; W-1121
W-1120
T-1010
T-1010
T-1010
T-1010
F-283
F-283
F-283
F-283
F-283
F-283
F-268
D-190
D-190
296
TABLE I I I
Transformat ions by Genus: ASPERGILLUS
SPECIES
ochraceus
ochraceus (Wilhelm)
*
*
SOURCE
ATCC-1009
C
C (924)
CZAA
IAM
IAM (mutant)
MCC
NRRL-405
SUBSTRATE
4-pregnene-3 ,20-d ione
20S-hydroxy-18,2G-cyclo-4-pregnen-3-one
18-hydroxy-4 -p regne^e -3 ,20-dione
6a - fluor o -1 la, 21 - dihy dr oxy -16a -methy l -4 -p regnene-3 , 20-dione
6a -fluor o -17a, 21 - dihy dr oxy -16a -methy l -4 -p regnene-3 , 20-dione 21-aceta te
4 -andros tene-3 ,17-d ione
3j3-hydroxy-5-pregnen-20-one
4-pregnene-3 ,2C-dione
4-pregnene-3 ,2C-dione
4-pregnene-3 ,20-d ione
16a, 17a-oxido-5a-pregnane-3,20-dione
4-pregnene-3 ,20-d ione
4 - e s t r e n e - 3 , 1 7 - d i o n e
17/3-hydroxy-4-estren-3-one
17ß-hydroxy-4-andros ten-3-one
6/3-hydroxy-3a, 5a-cyclo -pregnan-20-one
16a, 17a-oxido-5/3-pregnane-3, 20-dione
REACTION
l i a -OH
l i a - O H
l i a - O H
l i a - O H
l l a - O H ; 2 1 -OAc—21-OH
-
Δ 5 - Δ 4 ; 3/3-ΟΗ - 3 - C = 0
l l a - O H
l l a - O H ; 6/3, l l a -d iOH
l l a - O H (only)
l l a - O H
l l a - O H ; 6/3, l l a - d i O H
l l a - O H (High concentrat ion 30 - 50 g r a m s per l i ter)
l i a - O H
Πα-ΟΗ; 17/3-ΟΗ -» 1 7 - C = 0
11α-OH
11α-OH
11α-OH
R E F .
Μ-603
#-1071
W-1110
W-1098
W-1098
C-104
C-104
C-104
1-416; 1-417
1-416; 1-417
Κ-439; Κ-440
D-190
W-1067
D-150
D-150
S-835; V-1048
S-835
Κ-440; W-1066
TABLE I I I
T r a n s f o r m a t i o n s by Genus : ASPERGILLUS
297
SPECIES SOURCE SUBSTRATE REACTION REF.
ochraceus NRRL-405 4 -p regnene-3 ,20-d ione
4 ,16-pregnad iene-3 ,20-d ione
6a - f l uo ro -4 -p regnene -3 ,20 -dione
l i a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
17a -hydroxy-4 -p regnene -3 ,20 -dione
1 7 a - b r o m o - 4 - p r e g n e n e - 3 , 2 0 -dione
17a -methyl-4 -pregnene - 3 , 2 0 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
l i a - O H ; ( suppress ion of 6j3-OH - effect of zinc )
l i a - O H
l i a - O H (with conidia)
l i a - O H (continuous fermentation)
6j3, l la-diOH
6/3,1 la-diOH (with conidia)
l l a - O H ; 17/3-A c - 1 7 - C = 0
l l a - O H ; 17/3-Ac->17-C=0 (with conidia)
l l a - O H
6/3-OH
l l a - O H
l l a - O H
l l a - O H
l l a - O H
D-181
D-182 D-193 K-435 K-436 S-835 S-900 V-1C48; W-1065; W-1066
K-454; S-797
M-562
D-181 D-182 D-193 K-435 K-436 M-562 S-900 V-1048
S-797
V-1048
S-835
S-835; V-1048
V-1048
S-835; V-1048
S-835; V-1048
S-835; V-1048
D-182; D-193; S-835; V-1048
298
TABLE I I I
Transformat ions by Genus: ASPERGILLUS
SPECIES
ochraceus
oryzae
*
*
*
SOURCE
NRRL-405
SSSR(26)
CBS
CZAA
IAM
IAM (mutant)
IAM (24,31)
IAM ( 1 , 2 , 3 , 11 ,15,82)
IAM(24,31)
IAM( 24 )
IPB
SUBSTRATE
17a ,21-d ihydroxy-4-pregnene-3,20-dione
1 7 a , 2 1 - d i h y d r o x y - l , 4 - p r e g n a -d iene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
3j3,14j3-dihydroxy-5/3-20(22)-cardenolide
4 -andros tene-3 ,17-d ione
3/3-hydroxy-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
3/3,21-dihydroxy-5-pregnen-20-one 21 aceta te
21 -hydroxy-4 -p regnene -3 ,20 -dione
1 la, 21 -dihydr oxy -4 -pregnene -3,20-dione
4 -andr ostene -3 ,17 -dione
17/3-hydroxy-4-androsten-3-one
REACTION
l l ö - O H
l i a - O H
l l ö - O H ; 6/3, l lö -d iOH
3 / 3 - O H - 3 - C = 0
7/3-OH
17-C=0->17a-o x a - 1 7 - C = 0
Δ 5 - Δ 4 ; 3/3-ΟΗ -» 3-C = 0
17/3-Ac-17a-o x a - 1 7 - C = 0
l l o - O H ; 6/3, l l ö -d iOH
-
17/3 - A c - 17a-o x a - 1 7 - C = 0
17/3-Ac-» 17a-o x a - 1 7 - C = 0
3 /3 -OH-3-C=0; Δ5-»Δ4; 17/3-(20-C=O-21-OAc) —17a-o x a - 1 7 - C = 0
17/3-(20-C=O-2 1 - O H ) - 1 7 a -o x a - 1 7 - C = 0
-
1 7 - C = 0 —17/3-OH
1 7 - C = 0 - 1 7 a -o x a - 1 7 - C = 0
17/3-OH-17-C
=o
R E F .
D-182; D-193; K-435; K-436; S-835; V-1048
S-835; V-1048
T-1010
J-432
J-432
C-104
C-104
C-104
1-416; 1-417
1-416; 1-417
K-461
K-461
K-461
K-461
K-461
C-102
C-102
C-102; H-332
1
TABLE I I I
T r a n s f o r m a t i o n s by Genus : ASPERCILLUS
299
SPECIES
oryzae
1 *
I ost ianus
1 *
SOURCE
IPB
MCC
Sandoz NG
NI
SSSR
SSSR(17)
CZAA
SUBSTRATE
17/3-hydroxy-4-androsten-3-one
4 -p regnene-3 ,20-d ione
l l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
17ö-hydroxy-4-p regnene-3 ,20-dione
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
4 -p regnene-3 ,20-d ione
3/3, 6/3, 8/3,14/3-tetrahydroxy-4, 20,22 -bufatrienolide 6-aceta te 3-glucoside
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide 3-[glucosyl-digi toxosyl-digi toxosyl-digitoxoside]
17/3-hydroxy-4-androsten-3-one
4 -p regnene-3 ,20-d ione
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
4 -andros tene -3 ,17-d ione
3/3-hydroxy-5-pregnen-20-one
REACTION
17/3-OH-17a-o x a - 1 7 - C = 0
17/3-Ac-17/3-OH
17/3-Ac-17-
c=o 17/3-Ac—17a-o x a - 1 7 - C = 0
17 /3 -Ac-17 -C=0
17/3-Ac-17/3-OH
17a-OH-17/3-Ac - 1 7 - C = 0
17a-OH-17/3-Ac — 17/3-OH
17a-OH-17/3-Ac —17a-oxa-17-c=o 17/3-Ac—17-C=0
17/3-Ac-17/3-OH
l i a - O H
^ - [ l V g l u c o s i d e j — 3/3-OH
glucosyl-digitoxosyl-digitoxosyl-digitoxoside — digitoxosyl-digitoxosyl-digitoxoside
17/3-OH-1 7 - C = 0
l i a - O H ; 6/3, l l ö -d iOH
-
metaboli te - X
Δ 5 - Δ 4 ; 3/3-OH-3 - C = 0
R E F .
C-102
C-102
C-102
C-102; H-332
C-102; H-332
C-102; H-332
C-102
C-102
C-102; H-332
C-102
C-102
D-190
S-936a
S-936a
K-482
T-1010
T-1010
C-104
C-104
300
TABLE I I I
Transformat ions by Genus: ASPERGILLUS
SPECIES
ostianus
*
panamensis
pa ras i t i cus
*
*
penicil ioides
*
*
phoenicis
*
pro lifer ans
pseudoglaucus
*
pulverulentus
quadri l ineatus
*
rehmi i
SOURCE
CZAA
IAM
IAM
CZAA
IAM
MCC
CZAA
IAM
NRRL-1956
IAM
IAM
MCC
IAM
IAM
MCC
CZAA
SUBSTRATE
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -p regnene -3 , 20-dione
4 -andr ostene -3 ,17 -dione
3/3-hydroxy-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -andr ostene -3 ,17 -dione
3/3-hydroxy-5-pregnen-2 r -one
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
plant saponins
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -androstene -3 ,17 -dione
REACTION
metabolite - X
11α-ΟΗ; 6/3, ΙΙα-diOH
-
metabolite - X
Δ5 Δ4; 3/3-ΟΗ 3-C = 0
metabolite - X
11α-OK; 6/3, l lo -d iOH
-
1 7 - C = 0 - * 1 7 a -o x a - 1 7 - C = 0
Δ 5 - Δ 4 ; 3/3-OH -3-C = 0
17/3 - A c - 17a-oxa-17-C = 0
-
3/3-giycoside (saponin) —̂ 3/3-OH
3/3-glycoside (saponin) —»
3/3-OH
-
—
l l a - O K ; 6/3, l l a -d iOH
-
11a-OH; 6/3, l l a -d iOH
l l a - O H ; 6ß, l l a - d i O H
metaboli te - X
R E F .
C-104
1-416; 1-417
1-416; 1-417
C-104
C-104
C-104
1-416; 1-417
D-190
C-104
C-104
C-104
1-416; 1-417
K-478
K-479
1-416; 1-417 1-416; 1-417
D-190
1-416; 1-417
1-416; 1-417
D-190
C-104
301
TABLE I I I
Transformat ions by Genus: ASPERGILLUS
SPECIES
rehmi i *
repens *
r e s t r i c t u s
ruber
1 *
1 *
rugulosus
sai toi
sc le ro t io rum
1 *
1 *
I sojae *
SOURCE
CZAA
IAM
CZAA
MCC
CZAA
IAM
MCC
IAM
MCC
IAM (R-1216) (H-0756)
CZAA
IAM
IAM
IAM mutant
SUBSTRATE
3/3-hydroxy-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -andros tene -3 ,17-d ione
3/3-hydroxy-5-pregnen-20-one
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -andr ostene -3 ,17 -dione
3ß-hydroxy -5-pregnen-20-one
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4-andr os tene-3 ,17-d ione
3/3-hydroxy-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
REACTION
Δ5->Δ4; 3j3-OH - 3 - C = 0
metaboli te - X
l i a - O H ; 6/3, l l a - d i O H
metaboli te - X
Δ 5 ^ Δ 4 ; 3/3-OH ^ 3 - C = 0
metaboli te - X
l i a - O H
1 7 - C = 0 ^ 17a-o x a - 1 7 - C = 0
-
17/3-Ac-» 17a-o x a - 1 7 - C = 0
11a-OH; 6/3, l l a - d i O H
11a-OH; 6/3, l l a - d i O H
11a-OH; 6/3, l l a - d i O H
11a-OH
11a-OH
6/3-OH; 11a-OH
1 7 - C = 0 - 17a-o x a - 1 7 - C = 0
Δ 5 - Δ 4 ; 3/3-OH - 3 - C = 0
1 7 ß - A c - 1 7 a -o x a - 1 7 - C = 0
~
6 ß , l l a - d i O H
l i a - O H
R E F .
C-104
C-104
D-190; 1-416; 1-417
C-104
C-104
C-104
D-190
C-104
C-104
C-104
1-416; 1-417
D-190
1-416; 1-417
D-190
1-416; 1-417
1-416; 1-417
C-104
C-104
C-104
1-416; 1-417
1-416; 1-417
1-416; 1-417
302
TABLE I I I
Transformat ions by Genus: ASPERGILLUS
SPECIES
s p a r s u s
species *
sulphureus *
sydowi
*
*
t amar i i
SOURCE
IAM
MCC
NG
Sandoz NG (811,882, 883 ,888 ,895 , 906)
NG
PIRI
IAM
CZAA
IAM
MCC
CZAA
SUBSTRATE
4 - p r e g n e n e - 3 , 20 -dione
4-pregnene-3 ,20-d ione
1,3,5(10) - e s t r atriene-3/3,17/3-diol (sole carbon source)
3 - h y d r o x y - l , 3 , 5 ( 1 0 ) - e s t r a t r i e n -17-one (sole carbon source)
3/3,6/3,8/3,14/3-tetrahydroxy-4-20,22 -bufatrienolide 6-aceta te 3-glucoside
3/3,14/3-dihydroxy-5ß-20(22)-cardenol ide 3-[glucosyl-digi toxosyl-digi toxosyl-digitoxoside]
3-hydroxy-4-cholenic acid (sole carbon source)
3α,7α, 12a-trihydroxy-5/3-cholanic acid ( sole carbon source)
3/3-chloro-5-cholestene (sole carbon source)
5a, 6/3-dibromocholestan-3/3-ol aceta te ( sole carbon source)
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 - and ros t ene -3 ,17 -d ione
3/3-hydroxy-5-pregnen-20-one
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene -3 ,20 -dione
4 -andros tene-3 ,17-d ione
REACTION
-
l l a , 1 7 a - d i O H
—
3/3-[lVgluco-side] -^3/3-OH
glucosyl-digitoxosyl-digitoxosyl-digitoxoside —» digitoxosyl-digitoxosyl-digitoxoside
-
l l a - O H ; l i a , 2 1 -diOH
l l a - O H ; 6/3,11a-diOH
-
Δ ^ Δ 4 ; 3/3-ΟΗ-* 3 - C = 0
l l a - O H ; metaboli te - X
l l a - O H ; 6/3,11a-diOH
l l a - O H
R E F .
1-416; 1-417
D-180
T-1033
T-1033
S-936a
S-936a
T-1033
T-1033
T-1033
T-1033
W-1081
1-416; 1-417
C-104
C-104
C-104
1-416; 1-417
D-190
C-104
TABLE I I I
Transformat ions by Genus: ASPERGILLUS
303
SPECIES
t a m a r i i *
*
*
t e r r e u s
*
1 *
*
t e r r i c o l a
1 *
1 *
1 *
1 * unguis
1 *
SOURCE
CZAA
IAM (mutant)
MCC
NRRL (RBI)
CZAA
IAM (mutant)
MCC
MCC (MF-181)
NRRL
CZAA
IAM
MCC
IAM
MCC
NRRL
SUBSTRATE
3ß-hydroxy-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
Saponins (agave)
4 -andros tene -3 ,17-d ione
3/3-hydroxy-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
Dioscin
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
4 -andros tene -3 ,17-d ione
3j8-hydroxy-5-pregnen-20-one
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
Sarsasapogenin
REACTION
Δ5—Δ4; 3/3-OH - > 3 - C = 0
l i a - O H
l i a - O H ; 6/3, l l a - d i O H
l i a - O H
3/3-glycoside (saponin) -* 3/3-OH
1 7 - C = 0 ^ 1 7 a -o x a - 1 7 - C = 0
Δ5-*Δ4; 3/3-OH - 3 - C = 0
17/3-Ac-*17a-o x a - 1 7 - C = 0
l i a - O H ; 6/3, l l a - d i O H
l i a - O H ; 6/3, l l a - d i O H
3/3-glycoside —» 3/3-OH
-
-
—
1 7 - C = 0 - ^ 17a-o x a - 1 7 - C = 0
Δ 5 - Δ 4 ; 3/3-OH - 3 - C = 0
17/3-Ac^l7a-o x a - 1 7 - C = 0
l i a - O H ; 6/3, l l a - d i O H
l i a - O H
-
l i a - O H ; 6/3, l l a - d i O H
—
R E F .
C-104
C-104
1-416; 1-417
D-190
K-479
C-104
C-104
C-104
1-416; 1-417
D-190
R-781
M-587
M-587
M-587
C-104
C-104
C-104
1-416; 1-417
D-190
1-416; 1-417
D-190
M-587
304
TABLE I I I
Transformat ions by Genus: ASPERGILLUS
SPECIES
unguis
usami i
*
*
ustus
*
*
*
var ians *
var iecolor
*
*
vers ico lor
*
*
SOURCE
NRRL
IAM (B-407)
IAM (R-0635)
IAM (mutant)
(59-1)
ATCC-10032
CZAA
IAM
MCC
IAM
CZAA
IAM
MCC
CZAA
IAM
MCC
SUBSTRATE
Diosgenin
4 -dehydr otigogenone
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
21-hydroxy-4-p regnene-3 ,20-dione aceta te
4 -andr ostene -3 ,17 -dione
3ß-hydroxy-5-pregnen-20-one
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-andr os tene-3 ,17-d ione
3/3-hydroxy-5-pregnen-20-one
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -andr ostene -3 ,17 -dione
3ß-hydroxy-5-pregnen-20-one
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
REACTION
—
-
l i a - O H
l l a - O H ; 6/3, l l a -d iOH
l i a - O H ; 6/3, l l a - d i O H
l i a - O H
l i a - O H ; 21-OAc ^ 2 1 - O H
-
Δ5-*Δ4; 3/3-ΟΗ - 3 - C = 0
l i a - O H
l l a - O H ; 6/3, l l a - d i O H
l l a - O H
l l a - O H ; 6/3, l l a - d i O H
-
Δ5-*Δ4; 3/3-ΟΗ -» 3 - C = 0
l l a - O H
—
l l a - O H ; 6/3, l l a - d i O H
-
Δ 5 ^ Δ 4 ; 3β-ΟΗ - 3 - C = 0
l l a - O H ; metaboli te - X
l l a - O H ; 6/3, l l a - d i O H
l l a - O H
R E F .
M-587
M-587
1-416; 1-417
1-416; 1-417
1-416; 1-417
M-603
M-603
C-104
C-104
C-104
1-416; 1-417
D-190
1-416; 1-417
C-104
C-104
C-104
1-416; 1-417
D-190
C-104
C-104
C-104
1-416
D-190
305
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: ASPERGILLUS
AZOTOBACTER (Schizo. - Eubacteriales)
SPECIES
vers ico lor
violaceo-fuscus *
wentii
*
*
(in mixed cul ture with Agrobacter ium ethanicus)
AZOTOBACTER
agi l is
chroococcum
indicus
1 oxydans
SOURCE
SSSR(16)
IAM
ATCC-10583
IAM
IAM (mutant)
MCC
NRRL
NG
ATCC-9042
NG
ATCC-9037
ATCC-9540
NG
SUBSTRATE
4-pregnene-3 ,20-d ione
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
4 -p regnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
5-cholesten-3/3-ol
5-cholesten-3/3-ol ace ta te
24 /3-methyl -5 ,7 ,22-choles ta -tr ien-3/3-ol
4 , 4 , 1 4 a - t r i m e t h y l - 5 a , 8 ,24-cholestadien -3/3 -ol
24-e thyl -5 ,22-choles tadien-3/3-ol
11/3,17a, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
5-cholesten-3/3-ol
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
11/3,1 7a, 21 - t r ihydroxy-4 - p r e g -nene -3 ,20-d ione
5-cholesten-3/3-01
REACTION
6/3, l l a - d i O H
-
11a-OH; 6/3, l l a - d i O H
11a-OH
l l a - O H ; 6ß, l l a - d i O H
-
l l a - O H
-
-
-
degradation
degradation
degradation
degradation
degradation
Δ1
degradation
Δ1
Δ1
3/3-OH — 3 - C - O ; Δ5->Δ4; degradat ion
7
Δ
R E F .
T-1010
T-1010
1-416; 1-417
M-603
1-416; 1-417
1-416; 1-417
D-190
M-587
M-587
M-587
T-1015; T-1016
T-1015; T-1016
T-1015; T-1016
T-1015; T-1016
T-1015; T-1016
T-989
M-595
T-989
T-989
H-406; H-407
H-406; H-407 |
306
T r a n s f o r m a t i o n s by Genus:
TABLE I I I
AZOTOBACTER AZOTOMONAS
BACILLUS
TAXONOMY
(Schizo. - Pseudomonadales) (Schizo. - Eubacteriales)
SPECIES
spec ies
vinlandii
AZOTOMONAS
fluorescens
BACILLUS
alvei
b rev is
ce reus
SOURCE
NG
NG
ATCC-13544
IFO(3343)
IFO(333l )
IAM(B-204- l )
IFO
IFO (murao)
IFO (DC-3)
IFO (3001)
IFO (3015)
IFO (3039)
IFO (3131)
SUBSTRATE
5-cholesten-3j3-ol
5-cholesten-3/3-ol
17a, 21-d ihydroxy-4-pregnene-3,2C-dione
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
1 Ία, 21 -dihydroxy -4 -pr egnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17o, 21 -dihydroxy -4 -pregnene-3,20-dione
21-hydroxy-4-p regnene-3 ,20-dione
11/3,21-dihydroxy-4-pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pr egnene r 3 ,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
REACTION
Δ7; 3 / 3 - O H -3 - C = 0 ; Δ 5 - Δ 4 ;
degradation
degradation
Δ1
1
Δ
11a-OH
-
6/3-OH
11a-OH
6β-ΟΗ;11α-ΟΗ; 14a-OH
14a-OH; 11/3-OH -n-c=o Δ1; 6/3-OH; l l a - O H ; l l / 3 - O H
6/3-OH; l l a - O H
Δ1; 6/3-OH; l l a - O H ; 11/3-OH
l l a - O H
l l a - O H
l l a - O H
— 1
Δ
R E F .
H-406
M-595
T-989
T-989
S-849
S-849
S-944
S-944
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
TABLE I I I
307
T r a n s f o r m a t i o n s by Genus: BACILLUS
SPECIES
ce reus
(in mixed cul ture with Myococcus sp. A,)
1 c i rculans
(in mixed cul ture with Myococcus sp. A,)
c los teroides
coagulans
coli (communis)
Taxonomy - now considered in genus -Escher ich ia
fir mus
SOURCE
IFO (3466)
MCC (MB-718)
NRRL B-1666
NG
IFO (3029)
IFO (3329)
IFO(3342)
NG
ATCC-7050
IFO (P-22)
IFO (P-33)
IFO (P-55)
Feces
IFO (3330)
SUBSTRATE
l l ß , 1 7 a , 2 1 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
1 l a -hyd roxy -4 -p regnene -3 ,20 -dione
1 la, 21 -dihydroxy -4 -pregnene -3 ,20-dione
11/3,17«, 21 - t r ihydroxy-4 - p r e g -nene -3 ,20-dione
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
5-cholesten-3/3-ol (sole carbon source)
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
3 ,7 ,12- t r iketo-5/3-cholanic acid
3,7-diketo-5j3-cholanic acid
17α, 21 -dihydroxy -4 -pregnene -3 ,20-dione
REACTION
-
1
Δ
11a-OH
11a-OH
14a-OH
6/3-OH; l l a - O H
-
-
-
-
-
-
-
-
-
-
-
7 - C = 0 ^ 7 a - O H
3-C=0->3a-OH; 7 - C = 0 - 7 a - O H
—
R E F .
1-428
1-428
M-568
M-568
F-288
S-859
S-859
S-859
1-428
1-428
S-849
S-849
T-1030
S-849
S-849
S-849
S-849
F-289
S-899
S-849
308
TABLE I I I
T r a n s f o r m a t i o n s by Genus: BACILLUS
SPECIES
lentus
SOURCE
ATCC-13805 (mutant)
SUBSTRATE
3/3-hydroxy-5-androsten-17-one
3/3-hydroxy - 5 -androsten -17 -one aceta te
4 -andros t ene -3 ,17 -dione
D -homo -17a -oxa-4 -andros tene -3 ,17-dione
17/3-hydroxy-17a-methyl-4-andros ten-3-one
3 ,21-dihydroxy-16a, 17a-oxido-5-pregnen-20-one
17a,21 -d ihydroxy-4-pregnene-3,20-dione
1 la , 21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione
6 /3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
11/3, 17a ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-dione
12/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
14a, 17a ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
9a - f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
16a -methy l -4 -pr egnene - 3 , 2 0 -dione
17a-hydroxy-16a-methyl -4-pr egnene -3 ,11 ,20 - t r ione
21-hydroxy-16a-methy l -4-p regnene -3 ,11 ,20 - t r i one
17a, 21-dihydroxy-16a-methyl -4 -p regnene -3 ,11 ,20 - t r i one
9 a - f l u o r o - l l ß , 17a ,21- t r ihydroxy-16a -me thy l -4 -p regnene -3 ,20 -dione
l l ß , 17a-dihydroxy-16a-methyl-4-pregnene-3 ,20-d ione
11/3,21 -dihydroxy- 16a -methyl -4-pregnene-3 ,20-d ione
REACTION
Δ1; 3/3-OH -» 3 - C = 0 ; Δ 5 - Δ 4
Δ1; 3ß-OAc -» 3/3-OH; 3 ß - O H ^ 3 - C = 0 ; A 5 - A 4
1
Δ
Δ1
Δ1
3 /3 -OH^3-C=0 ; Δ 5 - Δ 4 ; Δ1
Δ1
Δ1
1
Δ j
Δ1
Δ1
1
Δ
Δ1
1
Δ
Δ1
1
Δ
Δ1
1
Δ
Δ1
Δ1
L
R E F .
R-750
R-750
R-750
R-750
R-750
R-750
R-750
R-750
R-750
R-750
R-750
R-750
R-750
R-750
R-750
R-750
R-750
R-750
R-750
R-750
TABLE I I I
309
Transformat ions by Genus: BACILLUS
SPECIES
lentus
mace rans (Schardinger)
(from leaves of Digitalis purpurea)
mega te r ium
SOURCE
ATCC-13805 (mutant)
NG
IFO(3483)
IFO(3490)
ATCC-13368 (SCH-41) (WC-41)
I F O ( 6 - l )
I F O ( 1 2 - l )
I F O ( 3 7 - l )
IFO(899- l )
IFO(EC-34)
SUBSTRATE
17ö, 21-d ihydroxy-16a-methyl -4 -p regnene-3 ,20-d ione
11/3,17a, 21 - t r ihydroxy-16a -methyl-4 -pregnene - 3 , 2 0 -dione
Digitonin
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
1 l a , 21 -d ihydroxy-4 -p regnene-3, 20-dione
4 -pregnene-3 ,20-d ione
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
17«, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r ione
l l a , 1 7 a , 2 1 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
11/3,17a, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
17a, 21 -dihydroxy -1 ,4 -pr egna -d i ene -3 ,11 ,20 - t r i one
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - l , 4 -pr egnadiene -3 ,20-dione
9a - f luo ro - l l / 3 ,16a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
9a - f luo ro - l l / 3 ,17a ,21 - t r ihydroxy-4-pregnene-3 ,20-d ione
17a,21 -d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
17a, 21 -dihydr oxy -4 -pregnene -3 ,20-dione
REACTION
Δ1
Δ1
3ß-glycoside (saponin) —» 3j3-OH
—
-
15/3-OH
15/3-OH
15/3-OH
15/3-OH
15j3-OH
Δ χ - Η
Δ1 — H
15β-ΟΗ
15j3-OH
11/3-OH; 2/3-OH
l l a - O H ; 6j3-OH
-
11a-OH
2/3-OH
R E F .
R-750
R-750
S-794
S-849
S-849
H-382
C-126; C-127; H-382
C-126
C-126
C-126; C-127
H-382
H-382
N-669
N-669
S-849
S-849
S-849
S-849
S-849
310
TABLE I I I
T r a n s f o r m a t i o n s by Genus : BACILLUS
SPECIES
megater ium
(in mixed cul ture with Mycobacter ium sp. )
mycoides
SOURCE
NG
NRRL
NRRL B-938
SSSR
NG
SUBSTRATE
5-cholesten-3/3-ol
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
4 - e s t r e n - 3 - o n e
16a-hydroxy-4-es t ren-3 -one
16/3-hydr oxy -4 - e s t r e n - 3 -one
4 - e s t r ene -3 ,16 -dione
4 -pregnene-3 ,20-d ione
21-hydroxy-4 -p regnene-3 ,20-dione ace ta te
17α, 21 -dihydr oxy-4-pregnene -3,20-dione 21-ace ta te
17α,21 -d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione 21-aceta te
17α, 21 -dihydroxy - 1 , 4 -pr egna -d i ene -3 ,11 ,20 - t r i one 21-aceta te
17a, 21 -dihydroxy - 5/3 -pr egnane -3 ,11 ,20 - t r ione 21-aceta te
17α, 20β, 21 - t r ihydroxy-4- p r e g -nene - 3 , 11-dione- 20, 21 -diacetate
16a, 17a-ox ido-4-pregnene-3 , 20-dione
5-cholesten-3/3-ol (sole carbon source)
2 4 - m e t h y l - 5 , 7 , 2 2 - c h o l e s t a -trien-3/3-ol
REACTION
—
-
-
-
16a-OH
16/3-OH
1 6 - C = 0 ; (via 16a-OH and 16/3-OH)
16a-OH -1 6 - C = 0
16a-OH -> 16/3-OH (via 16-C=0)
16/3-OH -» 1 6 - C = 0
1 6 - C = 0 -> 16/3-OH
15/3-OH
21-OAc -»21-OH
21-OAc—21-OH
21-OAC-21-OH
21-OAc—21-OH
21-OAC-21-OH
20ß-OAc-*20ß-OH; 21-OAc -» 21-OH; Δ1
2 0 - C = O - » 20a-OH
-
—
R E F .
T-1030
M-587
M-587
M-587
S-793a
S-793a
S-793a
S-793a
S-793a
S-793a
S-793a
D-191; M-568
S-948
S-948
S-948
S-948
S-948
S-917
S-947
T-1018
T-1018
TABLE I I I
311
T r a n s f o r m a t i o n s by Genus: BACILLUS
SPECIES
poly my xa
pro teus (See Genus - Pro teus )
pulvifaciens
SOURCE
IFO-3020
NRRL B-694
IAM (N-19-2)
SUBSTRATE
17a ,21-d ihydroxy-4-pregnene-3,20-dione
1 la, 21 -dihydroxy -4 -pr egnene -3,20-dione
3/3-hydroxy-5-androsten-17-one (or acetate)
17j3-hydroxy-4-androsten-3-one
6 /3-hydroxy-4-andros tene-3 ,17-dione
14ö-hydroxy-4 -andros t ene -3 ,17 -dione
3/3-hydroxy-5-pregnen-20-one
REACTION
-
—
3 ß - O H - 3 - C = 0 ; Δ 5 - Δ 4
Δ1; 3/3-ΟΗ -3 - C = 0 ; Δ 5 - Δ 4
Δ1; 3/3-OAc — 3/3-OH; 3/3-OH-3 - C = 0 ; Δ5->Δ4
3 ß - O H - 3 - C = 0 ; Δ 5 ^ Δ 4 ; 6/3-ΟΗ
14α-OH; 3/3-OH - * 3 - C = 0 ; A 5 - A 4
6/3-OH;X-OH; 3 ß - O H ^ 3 - C = 0 ; Δ5—Δ4
Δ ; Δ 5 - Δ ; 3 j3 -OH^3-C=0; 14α -OH
6-C = 0 ; 3j3-OH ->3-C=0 ; Δ 5 ^ 5ö-H
17/3-OH -> 1 7 - C = 0
17/3-OH -1 7 - C = 0 ; Δ1
Δ 4 - Δ 5 ; ketoniz.
Δ 1
3 j3 -OH^3-C=0; Δ 5 - Δ 4
R E F .
S-849
S-849
1-419; 1-420; T-1027
1-419; 1-420; T-1027
1-419; 1-420
1-419; 1-420; T-1027
1-419; 1-420; S-792; T-1027
S-792; T-1027
1-419; 1-420; S-792
1-419; 1-420; T-1027
1-419; 1-420
1-419; 1-420
1-419; 1-420
1-419; 1-420
1-419; 1-420; T-1027
312
TABLE I I I
T r a n s f o r m a t i o n s by G e n u s : BACILLUS
SPECIES
pulvifaciens
pumilus
putrif icus
pymilus
(in mixed cul ture with Mycococcus sp. AJ
ro seus
species
SOURCE
IAM (N-19-2 )
IAM
NG
IFO(3020)
IFO(3041)
IAM (B-A)
SUBSTRATE
3/3-hydroxy-5-pregnen-20-one
3/3-hydroxy-5-pregnen-20-one acetate
1 la, 21 -dihydroxy -4 -pr egnene -3,20-dione
11/3,21-dihydroxy-4-pregnene-3,20-dione
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene-3 ,11 ,20 - t r ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
4 -andros tene -3 ,17-d ione
17i3-hydroxy-4-androsten-3-one
4 -pregnene-3 ,20-d ione
11/3,17a, 21- t r ihydroxy-4-pr eg-nene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
11/3,21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
REACTION
3/3-OH—3-C=0; Δ 5 - Δ 4 ; Δ1
3/3-OAc—3-C=0; A 5 A 4
Δ —*Δ
3 / 3 - 0 A c - 3 - C = 0 ; Δ5->Δ4; Δ1
1
Δ
Δ1
Δ 1
1
Δ
-
Δ4 - 5 β - Η
Δ4 -5 /3-Η
Δ4 -5 /3-Η
-
1
Δ
1
Δ
1
Δ
Δ1
Δ1
1
Δ
1
Δ
R E F .
1-419; 1-420; Τ-1027
1-419; 1-420; Τ-1027
1-419; 1-420; Τ-1027
1-419; 1-420 Τ-1027
1-419; 1-420
1-419; 1-420; Τ-1019; Τ-1027
1-419; 1-420
S-849
Μ-545
Μ-545
Μ-545
1-428
1-428
S-849
S-848; S-849
S-848; S-849
S-848; S-849
S-848; S-849
S-848; S-849
TABLE I I I
313
T r a n s f o r m a t i o n s by G e n u s : BACILLUS
SPECIES
species
sphaer icus
SOURCE
NG
ATCC-245
ATCC-7054
ATCC-7055
SUBSTRATE
3/3-hydroxy - 5 -andros ten -17 -one
4 -andr ostene -3 ,17 -dione
4 -p regnene-3 ,20-d ione
17a -hydroxy-4 -p regnene-3 ,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
12a -ch lo ro -21-hydroxy-4 -p reg-n e n e - 3 , 1 1 , 2 0 - t r i o n e aceta te
17a ,21-d ihydroxy-6a ,16α-d i m e t h y l - 4 - p r e g n e n e - 3 , 1 1 , 20-t r ione
l l / 3 ,17a ,21- t r ihydroxy-16a-methyl-4 -pregnene - 3 , 2 0 -dione
12a- f luoro-21-hydroxy-4-preg-n e n e - 3 , 1 1 , 2 0 - t r i o n e 21-ace ta te
12a - f luo ro - l l ß ,21 -d ihydroxy-4-pregnene-3 ,20-d ione aceta te
5a -andros tane-3 ,17-d ione
5 ö - a n d r o s t a n e - 3 , 1 7 - d i o n e - l a -H3-
5 a - a n d r o s t a n e - 3 , 1 7 - d i o n e - l a -H2
5/3-androstane-3,17-dione
17/3-hydroxy-5a-androstan-3-one
17/3-hydroxy-1/3-methyl-5α-andros tan-3-one
5 a , 10a -es t r ane -3 ,17 -d ione
REACTION
Δ 5 - Δ 4 ; 3/3-ΟΗ— 3 - C = 0 ; 1 7 - C = 0 — 17/3-OH (anaerobic conditions)
17-C=0—17/3-OH (anaerobic conditions)
-
-
1
Δ
20-C=O -> 20/3-OH
Δ1; 21-OAc — 21-OH
Δ1
Δ1
Δ1; 21-OAc -> 21-OH
Δ1; 21-OAc -21-OH
1
Δ
Δ ' - ί Ια -Η 3 )
Δ ' - ί Ια -Η 2 )
-
Δ*; 17/3-OH-» 1 7 - C = 0
Δ1; 17/3-OH -1 7 - C = 0
—
R E F .
S-822
S-822
S-859
S-859
S-859
V-1045
W-1083
A-24; A-25
H-392
W-1083
W-1083
H-373; S-933
B-75a; G-323
R-768; R-769
S-933
H-373
H-373
S-933
314
TABLE I I I
T r a n s f o r m a t i o n s by G e n u s : BACILLUS
SPECIES
sphaer icus
SOURCE
ATCC-7055
SUBSTRATE
5 a - e s t r a n e - 3 , 17-dione
4 -andros tene -3 ,17 -dione
4 - a n d r o s t e n e - 3 , 1 7 - d i o n e - l a -H3
4 -andros tene -3 17-dione-1/3-H3
4 -andros tene -3 ,17 -dione - l a -H2
4 -andros tene -3 ,17-d ione - l /3 -H2
4 -andros tene -3 ,17 -dione -2 -H2
l a - h y d r o x y - 4 - a n d r o s t e n e - 3 , 1 7 -dione
2 /3-hydroxy-4-andros tene-3 ,17-dione
9a -hydroxy-4 -and ros t ene -3 ,17 -dione
9a, 18-dihydroxy-4-andros tene -3,17-dione
17/3-hydr oxy -4 -androstene -3 -one
17/3-hydroxy-4-estren-3-one
2α, 1 Iß -dihydroxy -4 -andr osten -3-one
2a, 17/3-dihydroxy-4-androsten-3-one diaceta te
2/3,17/3 -dihydroxy -4 -andr osten -3-one diaceta te
REACTION
Δ1
Δ1
A' ifrom l a - H 3 , 2/3-H)
Δ 1 ,
Δ 1
1
Δ
Δ1
-
1
Δ
Δ ; r e v e r s e aldol; enol.
Δ1; r e v e r s e aldol; enol.
Δ1; 1 7 / 3 - O H -1 7 - C = 0
Δ ; enol; 17/3-O H ^ 1 7 - C = 0
Δ 1 ; 17/3-OH — 17-C = 0
2a-OAc-» 2a-OH; 17/3-OAc^ 1 7 - C = 0
Δ1; 2a-OAc-> 2a-OH; 17/3-OAc-17 -C=0
2a-OAc-^2a-OH; 17ß-OAc — 17/3-OH
20-OAc -» 2/3-OH; 17/3-OAc -» 1 7 - C = 0
R E F .
S-933
H-373; H-399; S-933
B-75a; G-323
B-75a
R-469
R-469
R-469
H-373
H-373
K-473
K-473
H-373
G-317; S-933
G-318; H-373
H-399
H-399
H-399
H-399
TABLE I I I
315
T r a n s f o r m a t i o n s by G e n u s : BACILLUS
SPECIES
sphaer icus
(in mixed cul ture with Curvular ia l una t a - [ l lß-OH])
1 (in mixed cul ture 1 with Curvular ia
l una t a - [ l l ß -OH])
1 (in mixed cul ture 1 with Cunninghamella 1 b lakes leeana-Lend-
ner No. l[llß-OR])
(in mixed cul ture 1 with Cunninghamella
ech inu la t a - [ l l a -OH])
SOURCE
ATCC-7055
SUBSTRATE
2/3,17/3-dihydroxy-4-andr osten -3-one diaceta te
17/3-hydroxy-la -methyl-19 -nor -4 -andros ten-3-one
17ß-hydroxy-2a-methy l -4-andros ten-3-one
17a-ethinyl-9a-f luoro- l l /3 ,17/3-dihydroxy -4 -andr os ten- 3 -one
11/3,17/3-dihydroxy- 17a -methyl -4-andros ten -3-one
17a-ethinyl-17/3-hydroxy-4-andros tene-3 ,11-d ione
17a-ethinyl-11/3,17/3-dihydroxy -4 ,6 -andros tad ien-3 -one
17a-ethinyl-17/3-hydroxy-4,6-andros tad iene-3 ,11-d ione
17 /3-hydroxy-17a-methyl -4 ,9( l l ) -andros tad ien-3 -one
4 -p regnene-3 ,20-d ione
D-nor -4 -p regnene -3 ,20 -d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione aceta te
1 l a , 21 -dihydroxy -4 -pregnene -3 ,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
REACTION
2/3-OAc—2/3-OH; 17/3-OAc— 17ß-OH
Δ \ 17-
Δ \ 21
-
17/3- O H -■c=o
1
Δ
1
Δ
1
Δ
Δ1
1
Δ
Δ 1
Δ1
1
Δ
21-OAc — -OH
1
Δ
1
Δ
Δ1
Δ
1
Δ
R E F .
H-399
H-373
H-373
N-667
G-305
G-304
G-304
G-304
R-775
H-399
R-763
S-933
S-933
H-399; S-942
K-444
K-466
K-466
K-466
316
TABLE I I I
T r a n s f o r m a t i o n s by Genus: BACILLUS
SPECIES SOURCE SUBSTRATE REACTION R E F .
sphaer icus (in mixed cul ture with Stachylidium biocolor - [ l l a - O H , 11/3-OH])
in mixed cul ture with Vert ic i l l ium theobromae - [ l l a -OH, 11/3-OH])
ATCC-7055 17a, 21-dihydroxy-4-pregnene -3,20-dione
15)3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
11/3,17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
l i a , 15/3,17a,21-tetrahydroxy-4-pregnene-3 ,20-d ione
11)3,15/3,17a, 21 - te t rahydroxy-4-pregnene-3 ,20-d ione
17a-hydroxy-16-méthylène-4-pregnene-3 ,20-d ione aceta te
12a- f luoro- l l /3 ,21-dihydroxy-4-pregnene-3 ,20-d ione 2 1 -aceta te
12a - f luoro-21-hydroxy-4-preg-nene -3 , 11 ,20 - t r ione
17a, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r ione
17a, 21-dihydr oxy-4-pregnene-3 ,11 ,20 - t r ione 21-aceta te
15/3,17a, 21 - t r ihydroxy-4 -p reg -n e n e - 3 , l l , 2 0 - t r i o n e
7a, 17a, 21 - t r ihydroxy-4 -p reg -nene -3 ,11 ,20 - t r i one 2 1 -aceta te
17a, 21 -dihydroxy - 16a - methoxy -4 -p regnene -3 ,11 ,20 - t r i one
17a, 21-dihydr oxy-6a-methyl -4 - p r e g n e n e - 3 , 1 1 , 20- t r ione
17a, 21-dihydr oxy-16-méthylène-4-pregnene-3 ,20-d ione
17a ,21-d ihydroxy-16a-n i t ro-m e t h y l - 4 - p r e g n e n e - 3 , 1 1 , 2 0 -t r ione
K-468
K-468
C-126:
Δ1
Δ1
Δ1
Δ1
Δ1; 21-OAc 21-OH
Δ1
Δ1
Δ1
Δ1; 17a-(20-C=O-- 17-C=
1
Δ
Δ1; 21 -0 21-OH
1
Δ
Δ1
1
Δ
Δ1
OH 21-0
Ac
-
-17/3-OAc)
-
C-127
H-399; S-942
C-126; C-127
C-126; C-127
S-837
W-1083
W-1083
C-127
C-120
C-120
C-126
N-687
S-838
G-300
M-558
R-751
TABLE I I I
317
Transformat ions by Genus: BACILLUS
SPECIES
sphaer icus
SOURCE
ATCC-7055
SUBSTRATE
6a- f luoro-17a ,21-d ihydroxy-6a, 16a -d ime thy l -4 -p reg -n e n e - 3 , l l , 2 0 - t r i o n e 2 1 -aceta te
9a- f luoro-17a ,21-d ihydroxy-6a, 16a -d ime thy l -4 -p reg-n e n e - 3 , l l , 2 0 - t r i o n e 2 1 -aceta te
2a- f luoro-17a ,21-d ihydroxy-4 -pr egnene - 3 , 1 1 , 2 0 - t r ione
11/3,17a, 21- t r ihydroxy-16-methylene -4 -pr egnene -3 ,20 -dione
11/3,17a, 21- t r ihydroxy-16a-me thoxy-4 -p regnene -3 ,20 -dione
11/3,17a, 21 - t r ihydroxy -6a-methyl-4 -pr egnene -3 ,20 -dione
9a- f luoro- l l j3 ,17a ,21- t r ihydroxy-6 a - m e t h y l - 4 - p r e g n e n e - 3 , 2 0 -dione
11/3,17a, 21- t r ihydroxy-16a-nitr omethy 1-4-pr egnene-3,20-dione
9a- f luoro- l l /3 ,17a , 21 - tr ihydroxy-4-pregnene-3 ,20-d ione
12a - f l uo ro - l l / 3 , 17a ,21 - t r i -h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
9a- f luoro- l l /3 ,15 i3 ,17a ,21-t e t r ahyd roxy -4 -p regnene -3 , 20-dione
9a- f luoro- l l /3 ,15a , 16a, 2 1 -t e t r ahyd roxy -4 -p regnene -3 , 20-dione
9a- f luoro- l l /3 ,16a , 17a, 2 1 -t e t r a h y d r o x y - 4 - p r e g n e n e - 3 , 20-dione
9a- f luoro- l l j3 ,14a , 15j3,170,21-pentahydroxy - 4 - p r e g n e n e - 3 , 20-dione
17/3,20a-oxido -16-ox imino-4-pregnen-3-one
REACTION
Δ1; 21-OAc — 21-OH
Δ1; 21-OAc — 21-OH
1
Δ
1
Δ
1
Δ
Δ1
Δ1
Δ1
Δ1
Δ 1
Δ1
1
Δ
1
Δ
1
Δ
1
Δ
R E F .
A-24
A-25
H-401
T-981
S-838
G-300
G-300
R-751
N-669; S-942
H-380
N-669
N-669
H-399
N-669
N-686
318
TABLE I I I
T ransformat ions by Genus: BACILLUS
SPECIES
sphaer icus
SOURCE
ATCC-7055
ATCC-7063
ATCC-12488
SUBSTRATE
17/3,20a-oxido-16-oximino-5-pregnen -3/3-ol
21-hydroxy-17/3,20a-oxido-16-o x i m i n o - 4 - p r e g n e n e - 3 , 1 1 -dione
17a, 21 -d ihydroxy-4 ,6 -p regna-d i ene -3 ,11 ,20 - t r i one
17a, 21 -dihydroxy-4, 6 -pregna-d i ene -3 ,11 ,20 - t r i one 2 1 -aceta te
11/3,17a, 21 - t r i h y d r o x y - 4 , 6 -pregnadiene-3 ,20-d ione
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy-6a, 16a -dimethyl -4 -pregnene -3,20-dione 21-aceta te
17α-bromethinyl-17/3-methoxy -4 -andr osten - 3 - one
17α - chlor ethiny Ι-Πβ- methoxy -4-andros ten -3-one
17a-bromethinyl-6a-f luoro-17/3-methoxy-4-andros ten-3-one
17a-br omethiny 1 -17/3 - hydr oxy-6a -methy l -4 -andros ten -3 -one
17a -chlor ethiny 1 - 6a -f luor o -1 7/3- methoxy -4 -androsten -3-one
17a -chlor ethiny 1-17/3 -hydroxy -6 a - m e t h y l - 4 - a n d r o s t e n - 3 -one
17a -bromethinyl-6-chloro-17/3-methoxy-4 ,6 -androStadien -3-one
17a-bromethinyl -6- f luoro-17ß-methoxy-4 ,6-andros tad ien-3-one
17a-bromethinyl-17/3-hydroxy -6 -me thy l -4 ,6 -andros t ad ien -3-one
6-chloro-17a-chlor ethinyl-17/3-methoxy - 4 , 6 -andr os tadien-3-one
REACTION
Δ 5 ^Δ 4 ;3 /3 -ΟΗ^ 3 - C = 0 ; Δ 1
Δ1
1
Δ
Δ ; 21 -OAc -» 21-OH
1
Δ
Δ1; 2 1 - O A c -21-OH
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
R E F .
N-686
N-686
G-310
G-310
G-310
A-24; A-25
0-694; 0 -695
0-694; 0 -695
0-694 ; 0 -695
0-694; 0 -695
0-694; 0 -695
0-694; 0 -695
0-694 ; 0 -695
0 -694 ; 0 -695
0-694 ; 0 -695
0 -694 ; 0 -695
TABLE I I I
319
T r a n s f o r m a t i o n s by G e n u s : BACILLUS
SPECIES
sphaer icus
SOURCE
ATCC-12488
EM
EM(lOOl)
IFO
MCC
SUBSTRATE
17a-chlor ethiny 1-6-flu or o-17/3-methoxy-4 ,6 -andros tad ien-3-one
1 la -chlor ethinyl-17/3 -hydroxy -6 - m e t h y l - 4 , 6 - andros tadi en-s ' one
l l ß , 1 7 a , 2 1 - t r i h y d r o x y - 6 -methy lene -4 -pr egnene - 3 , 2 0 -dione
l l / 3 ,17a ,21- t r ihydroxy-16a-methy l -6 -mé thy lène -4 -pregnene-3 ,20-d ione
1 la, 21 -dihydr oxy -16 - méthylène -4 -p regnene-3 ,20-d ione
11/3,17a,21- t r ihydroxy-16-methy lene -4 - p r e g n e n e - 3 , 2 0 -dione
9a - f luo ro - l l /3 ,17a ,21- t r ihydroxy-16 - méthylène -4 -pregnene -3 ,20-dione
1 la -hydroxy -16 -méthylène - 4 -p regnene-3 ,20-d ione
11/3,1 la -dihydr oxy -16 - méthylène -4 -p regnene-3 ,20-d ione
9a- f luoro- l l /3 ,17a-d ihydroxy-16-methylene -4 -p regnene -3 ,20 -dione
14r*-hydroxy-4-andros tene-3 ,11 , 17-tr ione
17a, 21 -dihydr oxy -4 -pregnene -3 ,20-dione
4 -andr ostene -3 ,17 -dione
4 -p regnene-3 ,20-d ione
11/3-hydr oxy-4-pr egnene -3 ,20 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
21 -hyd roxy -4 -p regnene -3 ,11 , 20- t r ione
11/3,21-dihydroxy-4-pregnene-3,20-dione
REACTION
Δ1
1
Δ
Δ1
1
Δ
1
Δ
Δ1
1
Δ
Δ1
Δ1
Δ1
Δ1
—
Δ1
1
Δ 1
Δ
1
Δ
1
Δ
Δ 1
R E F .
0 -694 ; 0 -695
0 -694 ; 0 -695
F-264
F-264
M-558
M-558
M-558
B-68
B-68
B-68
T-955
S-849
S-942
S-942
S-942
S-942
S-942
S-942
320
TABLE I I I
T r a n s f o r m a t i o n s by G e n u s : BACILLUS
SPECIES
sphaer icus
SOURCE
MCC
MCC MB (431)
NG
SUBSTRATE
1 la, 21 -dihydr oxy -4 -pr egnene -3,20-dione
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
9a - f luoro - l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
12a -fluor o -11/3,21 -dihydroxy -4 -pregnene-3 ,20-d ione
12a-f luoro- l l /3 ,21-dihydroxy-4-pregnene-3 ,20-d ione 21-aceta te
1 la, 21 -dihydroxy -16 - méthylène -4 -p regnene -3 ,11 ,20 - t r i one 21-aceta te
l l / 3 ,17a ,21- t r ihydroxy-16-methylene -4 -pr egnene - 3 , 2 0 -dione 21-aceta te
11/3,17a,21-trihydroxy-16/3-me thy l -4 -p regnene -3 ,20 -dione 21-aceta te
9a - f luoro - l l /3 ,17a ,21- t r ihydroxy-16/3-methyl-4-pregnene-3,20-dione 21-aceta te
9a - f luoro- l l /3 ,17a ,21- t r ihydroxy-16 - méthylène -4 -pr egnene -3,20-dione 21-aceta te
12a - f luoro-21-hydroxy-4-preg-nene -3 , 11 ,20 - t r i one aceta te
12a- f luoro- l l /3 ,21-dihydroxy-4-pregnene-3 ,20-d ione 2 1 -aceta te
11/3,1 la, 21 - t r ihydroxy -4 -pr eg-nene -3 ,20-dione
5a-andros tane-3 ,17-d ione
5a - andr o stane - 3 , 1 7 - dione - la - H
4 -andr ostene -3 ,17 -dione
4 -andr ostene -3 ,17 -dione - l a -H3
deu te r ioandros tene-3 ,17-d ione
4-androstene-3,17-dione-6/3-H2
REACTION
1
Δ
1
Δ
1
Δ
1
Δ
Δ1; 21-OAc -21-OH
Δ1; 21-OAc -21-OH
Δ1; 21-OAc -> 21-OH
Δ ; 21-OAc -» 21-OH
Δ1; 21-OAc — 21-OH
Δ1; 21-OAc -> 21-OH
Δ1; 21-OAc -» 21-OH
Δ1; 21-OAc — 21-OH
Δ 1 (vitamin K2 (35) identified a s co-factor)
1
Δ
Δ Μ Ι α - Η 3 ) 1
Δ
Δ Μ Ι Γ Ο Π Ι 1α-Η , 2/3-Η)
Δ (cell free)
Δ (cell free)
R E F .
S-942
S-942
S-942
T-984
T-985
W-1083a
W-1083a
T-986; T-987
T-986
W-1083a
W-1083
W-1083
G-291
H-375
G-323
H-375
G-323
M-535
M-535
TABLE I I I
321
T r a n s f o r m a t i o n s by Genus: BACILLUS
SPECIES
sphaer icus
subti l is
SOURCE
NG
IAM (ACTU-B-3-3)
(ACTU-B-3-4)
(ACTU-B-3-5)
(ACTU-B-5-6)
(Hay-1)
(Hay-2)
(Hay-3)
(Hay-4)
(Hay-5)
(Hay-6)
(Hay-8)
IFO(3026)
IFO(3027)
IFO(3033)
IFO(3035)
IFO( 3036 )
SUBSTRATE
4 -p regnene -3 ,20 -d ione -7a -H 3
4 -pr egnene -3 ,20 -dione - 16a -H3
4 - p r e g n e n e - 3 , 2 0 - d i o n e - l l a - H 3 , 12a-H3
4 -p regnene-3 ,20-d ione 20-cycloethyleneketal
11/3,17a,21-trihydroxy-12/3-methyl-4 -pregnene - 3 , 2 0 -dione 21-aceta te
17α, 21 -dihydroxy -4 -pregnene -3,20-dione
17α, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3, 20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
REACTION
Δ1
1
Δ
Δ1
1
Δ
Δ1; 2 1 - O A c ^ 21-OH
2/3-OH
2/3-OH
2/3-OH
2/3-OH
2β-ΟΗ; l i a - O H
2/3-OH
2/3-OH
2/3-OH
2/3-OH
2/3-OH
2/3-OH; l i a - O H
2/3-OH
-
Δ1; l l a - O H
-
2β-ΟΗ; l l a - O H
R E F .
G-323
G-323
G-323
F-251
C-131
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
322
TABLE I I I
T r a n s f o r m a t i o n s by Genus: BACILLUS
SPECIES
subti l is
SOURCE
IAM (Natto-1-2)
(Natto-1-3)
(Natto-1-4)
(Natto-1-5)
(Natto-1-6)
(Natto-1-7)
(Natto-1-8)
(Natto-1-9)
(Natto-1-10)
UNTatto-II-l)
NRRL-B-558
(PCI-219)
(PCI-220)
NG
SUBSTRATE
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
1 la, 21 -dihydroxy - 4 -pregnene -3,20-dione
17a,21 -d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a,21 -d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
l l / 3 ,17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
17a, 21 -dihydroxy -4-pregnene -3 ,11 ,20 - t r ione
REACTION
-
-
2/3-OH
2/3-OH
-
-
2/3-OH
l i a - O H
l l a - O H
-
1
Δ
1
Δ
2ß-OH
1 1
Δ (yield of Δ inc reased if grown in mixed cul ture with Rhizopus nigr icans)
2 0 - C = O -20/3-OH
1
Δ
1
Δ
Δ1; 20-C = O - * 20/3 -OH
R E F .
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
S-849
L-521; L-522
L-522
L-521; S-801
L-521 ; S-801
L-522
323
T r a n s f o r m a t i o n s by Genus:
TABLE I I I
BACILLUS BACTERIUM
TAXONOMY
(Schizo. - Eubacter ia les)
SPECIES
subti l is
thiaminolyticus
tumescens
BACTERIUM
bifidum (genus and spec ies changed to Lac to-
1 bacil lus parabifidus)
1 cyclo-oxydans
SOURCE
NG
NRRL
IAM
NG
NG
ATCC-12673
SUBSTRATE
3a, 7a, 12a-tr ihydroxy-5/3-cholanic acid (sole carbon source)
5-cholesten-3/3-01 (sole carbon source)
2 4 - m e t h y l - 5 , 7 , 2 2 - c h o l e s t a -trien-3/3-ol (sole carbon source)
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
17α, 21 -dihydroxy -4 -pr egnene -3,20-dione
5-cholesten-3/3-01 (sole carbon source)
5-cholesten-3/3-01
17/3-hydroxy-4-androsten-3-one
A -nor_-17/3 - hydr oxy - 3 - andr os ten-2-one
3/3-hydroxy-9,10-seco-1,3 ,5(10) -andros ta t r i ene -9 ,17-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione 20-cycloethyleneketal
REACTION
-
—
-
-
-
-
—
—
—
1
Δ
9a-OH
9a-OH (use of inhibi tors for Δ1)
9a-OH; 17/3-O H - 1 7 - C = 0
degradation (product -3aa-H-4a-7a/3-methyl -hexa-h y d r o - 1 , 5 -indane-dione)
Δ1; 20-C = O ^ 20ß-OH
1 Δ
9α-OH
Δ1
REF.
N-675
T-1018; T-1030
T-1018
M-587
M-587
M-587
S-849
T-1030
S-914
S-890
P-740
S-898
S-885
S-985
F-251
S-980; T-1005
S-885
F-251
324
TABLE I I I
T r a n s f o r m a t i o n s by Genus : BACTERIUM
SPECIES SOURCE SUBSTRATE REACTION R E F .
cyclo-oxydans ATCC-12673 1 l a -hyd roxy -4 -p regnene -3 ,20 -dione
16α, 17a-dihydroxy-4-pregnene -3,20-dione
1 la, 21 -dihydroxy -4 -pregnene -3 ,20-dione
17α, 21 -dihydroxy -4 -pregnene -3 ,11 ,20- t r ione
6a-f luoro-16a, 17a-dihydroxy -4-pregnene-3 ,20-d ione 16, 17-phenylcyclophosphate
16a, 17a-dihydroxy-6/3-methyl -4 -pregnene-3 ,20-d ione 16, 17 -phenylcyclophosphate
16a, 17a-d ihydroxy-4 ,6-pregna-d iene-3 ,20-dione 16 ,17-phenylcyclophosphate
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione (Ref. F-231 r e f e r s to use of dry cel l ma te r i a l r a the r than free growing cells)
ί ϊ /3,17α, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione 21-aceta te
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy 4-pregnene-3 ,20-d ione
1 2 a - c h l o r o - l l j 3 , 1 6 a , 1 7 a , 2 1 -t e t r ahydroxy-4-p regnene-3,20-dione 16, 17-cyclo-sulfate 21-aceta te
9a - f l uo ro - l l j 3 , 16a ,17a ,21 -te t rahydroxy-4-pregnene-3,20-dione
K-480
Δ1; 20-C^ 20j3-OH
Δ1
l
Δ
1
Δ
1
Δ
=o - K-480
F-258; F-259
K-480
K-480
F-259
F-259
F-259
F-231; F-232; K-480; R-779
K-480
K-480
F-262
G-296; G-297; L-505; R-779; S-890; S-908
Δ ; 1 6 a , 1 7 a , 2 1 -t r i O H - 2 0 - C = O -» 16a ,17aa-dihydroxy-17a/3-hydroxymethyl-D -homo-17 -C= O
G-297
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
TABLE I I I
325
T r a n s f o r m a t i o n s by Genus: BACTERIUM
SPECIES
cyclo-oxydans
havaniensis
SOURCE
ATCC-12673
ATCC-4001
SUBSTRATE
9a - f luo ro - l l / 3 ,16α ,17α ,21 -t e t r ahydroxy-4 -p regnene -3,20-dione
6 a - f l u o r o - l l a , 16α, 17α, 2 1 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione 16,17-acetonide
1 2 a - c h l o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione 16,17-cyclobenzyl-phosphonate 21-aceta te
9a- f luoro- l l /3 ,16a , 17a, 20/3,21 -pentahydroxy-4-pregnen-3-one
9a- f luoro- l l /3 ,16a , H a ^ l - t e t r a -hydroxy -1 ,4 -pr egnadiene -3,20-dione
9 a - f l u o r o - l l ß , 16α, 17α, 20/3,21-pen tahydroxy-1 ,4 -p regna-dien-3-one
5-cholesten-3/3-ol
4 -p regnene-3 ,20-d ione
1 l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
l l a - h y d r o x y - 1 6 a , 1 7 a - o x i d o -4-pregnene-3 ,20-d ione
21-hydroxy-16a ,17a-ox ido-4-pregnene-3 ,20-d ione ace ta te
16a, 21 -d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydr oxy-4 -p regnene-3,20-dione
REACTION
20-C=O-> 2 0/3-OH
Δ1; 20-C = O -20/3-OH
1
Δ
1
Δ
1
Δ
Δ1; 20/3-OH — 20-C=O
Δ ^ Η
20-C=O-> 20/3-OH
Δ ' - Η ; 20-C=O -20/3-OH
Δ ^ Η
20/3-OH -> 20-C=O
Δ 5 - Δ 4 ; 3/3-OH - 3 - C = 0
Δ1
Δ1
Δ1
Δ 1
Δ
Δ1
Δ1
R E F .
G-296
S-908
D-159
F-263
G-294; G-296
G-294; G-296
G-296
G-296; S-908
G-296
G-296
G-294; G-296
T-1005
F-233
F-233
F-233
F-233
F-233
F-233
F-233
326
TABLE I I I
T r a n s f o r m a t i o n s by G e n u s : BACTERIUM
SPECIES
havaniensis
mycoides
SOURCE
ATCC-1004
ATCC-4004
SUBSTRATE
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
16a, 17a ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
9a- f luoro- l l /3 , 16«, 17a - t r i -hydroxy-4 -p regnene-3 ,20-dione
9a - f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
9a-fluoro-11/3,17ö, 21- t r ihydroxy-4-pregnene-3 ,20-d ione 2 1 -aceta te
3 /3 ,16a,17a,21- te t rahydroxy-9 ( l l ) -5a -p regnen -20 -one 3/3,21-diacetate
11/3,16a, 17a, 21 - te t rahydroxy-4-pregnene-3 ,20-d ione
9 a - f l u o r o - l l j 3 , 1 6 a , 1 7 a , 2 1 -t e t r ahydroxy-4-p regnene-3,20-dione
4-pregnene-3 ,20-d ione
1 l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
l l a - h y d r o x y - 16a, 17a-oxido-4-pregnene-3 ,20-d ione
16a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
l l / 3 ,17a ,21 - t r ihydroxy-4 -pregnene-3 ,20-d ione
16a ,17a ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
9a- f luoro- l l /3 ,16a , 17a - t r i -hydroxy-4 -p regnene -3 ,20 -dione
9a - f l uo ro - l l j 3 , 17a ,21 - t r i -hydroxy-4 -p regnene -3 ,20 -dione
9 a - f l u o r o - l l / 3 , 1 7 a , 2 1 - t r i -hydroxy-4 -p regnene -3 ,20 -dione 21-aceta te
REACTION
Δ1
1
Δ
1
Δ
1
Δ
Δ ; 21-OAc -» 21-OH
1
Δ
3j3-OAc-*3-C = 0 ; Δ 1 ' 4 ; 21-OAc -» 21-OH
1
Δ
1
Δ
1
Δ
Δ1
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
Δ1; 21-OAc -» 21-OH
R E F .
F-233
F-233
F-238
F-233
F-233
F-233
O-705
F-233
F-233
F-240
F-240
F-240
F-240
F-240
F-240
F-240
F-238
F-240
F-240
327
TABLE I I I
T r a n s f o r m a t i o n s by Genus: BACTERIUM BASIDIOBOLUS
BEAUVERIA
TAXONOMY
(Phyco. - Entomophthorales) (Imperf. - Moniliales)
SPECIES
mycoides
(in mixed cul ture with Mycococcus sp. )
species (Schatz) 303
genus incor rec t * (gram posit ive coccus)
s te ro id ic las ium
BASIDIOBOLUS
rana rum (Eidam)
BEAUVERIA
bass iana
spec ies
SOURCE
ATCC-4004
IFO(3040)
LED
NG
NG
NG
CBS
FRI
ATCC-13144
SUBSTRATE
9a - f luo ro - l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione 2 1 -aceta te
l l / 3 , 16a ,17a ,21 - t e t r ahyd roxy -4 -pregnene-3 ,20-d ione
9 a - f l u o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione
1 I ß , 17a ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
l l / 3 , 17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
5-cholesten-3j3-ol
5-cholesten-3/3-01 (sole carbon source)
SEE UNIDENTIFIED GENUS
1,3,5(10) - e s t r a t r i ene -3,17/3-diol
3/3-hydroxy-5-androstene-17-one
4 -andros tene -3 ,17-d ione
5-cholesten-3/3-ol
17û, 21-dihydr oxy-4-pregnene-3,20-dione
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
1 Ία, 21 -dihydroxy -4 -pregnene -3 ,20-dione
REACTION
1
Δ
1
Δ
1
Δ
-
1
Δ
1
Δ (dry thalli)
1
Δ
-
util ization
17/3-OH -> 17-C = 0
degradation
degradation
-
6-OH; l i a - O H
11α-OH
11α-OH
R E F .
F-240
F-240
F-240
1-428
1-428
F-231
F-232
T-1030
M-595
E-194
A-23
A-23
A-23
A-23
W-1073
S-849
1-421
328
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: BEAUVERIA
BLAKESLEA BOLETINUS
BOLETUS
(Phyco. - Mucorales) (Basidio. - Agaricales) (Basidio. - Agaricales)
SPECIES
species
BLAKESLEA
t r i s p o r a
BOLETINUS
pictus
BOLETUS
acidus
amer icanus
SOURCE
ATCC-13144
SSSR
AL (F-12)
AL (H-35)
AL (G-119)
SUBSTRATE
16a- t -bu ty l -17a ,21-d ihydroxy-5a-pregnane-3 ,20-d ione
17a ,21-d ihydroxy-16a-methyl -5a-pregnane-3 ,20-d ione
16/3-ethyl-17a, 21-dihydroxy-5a-pregnane-3 ,20-d ione
17a,21-dihydroxy-16/3-methyl-5a-pregnane-3 ,20-d ione
17a ,21-dihydroxy-16a-methyl -4-pregnene-3 ,20-d ione
17a, 21-dihydroxy-16/3-methy 1-4 -pregnene-3 ,20-d ione
17a, 21-dihydroxy-16/3-methyl-4-pregnene-3 ,20-d ione 21-aceta te
17a, 21 -dihydroxy -1 ,4 -pr egna-d i ene -3 , 20-dione
16a - t -bu ty l -17a ,21 -d ihyd roxy - l , 4 -pregnadiene-3 ,20-d ione
17a ,21-d ihydroxy-16a-methy l - l , 4 -pregnadiene-3 ,20-d ione
16/3-ethyl-17a, 21-d ihydroxy-1 ,4 -pregnadiene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene-3,20-dione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ? 20-d ione
REACTION
11a-OH
11a-OH
11a-OH
11a-OH
11a-OH
11a-OH
l l a - O H ; 2 1 -O A c - 2 1 - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H ; 11/3-OH; 6/3-OH
-
-
R E F .
1-421
1-421
1-421
1-421
1-421
1-421
1-421
1-421
1-421
1-421
1-421
E-224
S-825
S-825
S-825
329
TABLE I I I TAXONOMY
BOLETUS BOTRYODIPLODIA
BOTRYTIS (Imperf. - Sphaeropsidales) (Imperf. - Moniliales)
SPECIES
lute us
1 BOTRYODIPLODIA
theobromae
BOTRYTIS
c inerea
SOURCE
AL (H-11)
AMCY
ATCC-12481
ATCC
S
TNAES
SUBSTRATE
4-pregnene-3 ,20-d ione
16a, 17a-oxido-4-pregnene - 3 , 2 0 -dione
17a, 21 -dihydroxy - 4 - p r e g n e n e - 3 , 20-dione
17a, 21-d ihydroxy-4-pregnene-3 , 20-dione 21-aceta te
4-pr egnene-3 ,20-dione
17a, 21-d ihydroxy-4-pregnene-3 , 20-dione
17a ,21-d ihydroxy-4-p regnene-3 , 20-dione 21-aceta te
17a -hydroxy-4 -p regnene -3 ,20 -dione
2 1 - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
1 Iß, 21 -dihydroxy-4 -pregnene - 3 , 20-dione
17 ,21-d ihydroxy-4 -p regnene-3 ,20-dione
17a -hydroxy-4 -p regnene-3 ,20-dione
REACTION
6/3,1 la -d iOH
l i a - O H
11/3-OH
11/3-OH; 21-OAc —21-OH
l l a - O H
11/3-OH
l l a - O H
Iij3-QH
11/3-OH; 1 1 -C = 0 ( v i a l l ß - O H )
11/3-OH; 11-C = 0(via 11/3-OH); 21 -OAc-21 -OH
11/3-OH; 1 1 - C = 0 (via 11/3-OH)
6/3-OH
6/3-OH
15/3-OH
15/3 -OH
15/3-OH; 11/3-OH—11-C=0
6/3-OH
11/3-OH
6/3-OH
R E F .
S-825
P-746
F-229
F-229
C-98
C-98
C-98
C-98
C-98
C-98
C-98
S-842
S-842
S-842
S-842
S-842
S-842
S-842
S-849
T r a n s f o r m a t i o n s by Genus:
330
TABLE I I I
T r a n s f o r m a t i o n s by G e n u s : BOTRYTIS
SPECIES
cinerea
fabae
paeoniae
reptons
1 species
1 spectabi l is
SOURCE
TNAES
TNAES (CI - 17)
UCT
S
TNAES (PI -1)
ATCC-12482
FRI
NRRL
NRRL
SUBSTRATE
21-hydroxy-4 -p regnene-3 ,20-dione
11)3,21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
4-pregnene-3 ,20-d ione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione 21-aceta te
4 -pregnene-3 ,20-d ione
17a-hydroxy-4-p regnene-3 ,20-dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17/3-hydroxy-4-estren-3-one
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
plant saponins
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
REACTION
6/3-OH; 11/3-OH
11/3-OH - » I l - C = 0 ; 1 5 j 3 -OH
2/3-OH; 6/3-OH; 11/3-OH
6/3-OH; 11/3-OH
l i a - O H
11/3-OH
l i a - O H
11/3-OH
11/3-OH; 11-C = 0 (via 11/3-OH)
11/3-OH; 21-OAc - 2 1 - O H
11/3-OH; 1 1 - C = 0 (via l l ß -OH) ;
21-OAc-21-OH
-
-
l i a - O H
11)3-OH
2/3-OH
10/3-OH
11/3-OH
6/3-OH;lla-OH
-
-
-
—
R E F .
S-849
S-849
S-849
S-849
C-98
C-98
C-98
C-98
C-98
C-98
C-98
S-859
S-859
S-859
S-859
S-849
D-150
F-229
S-849
K-478
M-587
M-587
M-587
331
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: BYSSOCHLAMYS CALONECTRIA
^Asco. - Endomycetales) (Asco. - Eypocrea les)
SPECIES
BYSSOCHLAMYS
nivea
CALONECTRIA
decora
(in sequential fermentat ion with one or more of the following cu l tu re s : Curvular ia lunata, Cunninghamella b lakes leeana, Curvular ia brachy-spora and T r i -cothecium roseum)
(in sequential fermentation with one or more of the following cu l tu res : Curvular ia lunata, Cunninghamella b lakes leeana, Curvular ia b rachy-spora and T r i -cothecium roseum)
SOURCE
FRI
C
SUBSTRATE
17a ,21-d ihydroxy-4-pregnene-3 , 20-dione
5o-andros tane-3 ,17-d ione
3ß-hydroxy - 5 -andros ten -17 -one
4 -andros tene -3 ,17-d ione
11/3,17a, 21- t r ihydroxy-5a-pregnane-3 ,20-d ione
17a, 21 - dihy dr oxy - 5a -pr egnane -3 ,11 ,20 - t r ione
17a, 21-dihy dr oxy-5/3-pr egnane -3 ,11 ,20 - t r ione
3/3-hydroxy-5-pregnen-20-one
3/3,21 -dihydroxy-5 -pregnen -20-one
4 -pregnene-3 ,20-d ione
l l / 3 -hydroxy-4 -p regnene-3 ,20-dione
REACTION
-
i , 4
Δ '
-1
Δ ! > 4
Δ
! , 4 Δ
1 . 4
Δ '
-
—
Δ1
Δ1; 17ß-Ac -» 1 7 - C = 0
1
Δ
1
Δ
R E F .
S-849
W-1096
W-1096
W-1096
W-1096
W-1096
W-1096
W-1096
W-1096
W-1096; V-1053
V-1053
W-1107
W-1107
332
TABLE I I I
T r a n s f o r m a t i o n s by Genus: CALONECTRIA
SPECIES SOURCE SUBSTRATE REACTION R E F .
decora
(in sequential fermentation with one or more of the following cu l tu res : Curvular ia lunata, Cunninghamella blakesleeana, Curvular ia b rachy-spora and T r i -cothecium roseum)
CBS
21-hydroxy-4-p regnene-3 ,20-dione
1 l a , 21 -dihydroxy -4 -pregnene -3,20-dione
1 Iß , 21-dihydroxy-4-pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene-3,20-dione
21 -hydroxy-4 -p regnene -3 ,11 , 20- t r ione
17a, 21-d ihydroxy-4-pregnene-3 ,11 ,20- t r ione
11a, 17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
11/3,17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
6a -f luoro-17a-hydroxy-16a -me thy l -4 -p regnene -3 ,20 -dione
l l j3 ,21-d ihydroxy-3 ,20-dike to-4-pregnen-18-a l (18—»11) hemiaceta l
l l ß , 1 7 a , 2 1 - t r i h y d r o x y - 3 , 2 0 -d ike to-4-pregnen-18-a l (18—»11) hemiaceta l
17j3 -hydr oxy - 7a - methyl -thio -4-androsten -3-one aceta te
14/3-hydr oxy-3 -keto-5ß-20(22) -cardenolide
3a, 14/3 -dihydroxy -5/3 -20(22)-cardenolide
7a-SCH3 -» 7a-S(0)CH3; 17ß-OAc -> Πβ-ΟΕ
12/3-OH
3a-OH-»3-C=0
3a-OH—3-C=0; 12/3-OH
V-1053; W-1096
W-1107
W-1096
V-
w V-
w w
V-
w
1053; -1096
1053; -1096
-1096
1053; -1096
W-1096
W-1096
W-1090a
W-1096; W-1104
W-1096
H-405
N
N
N
-677
-681
-681
c
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
TABLE I I I
T r a n s f o r m a t i o n s by Genus : CALONECTRIA
333
SPECIES SOURCE SUBSTRATE REACTION REF.
decora CBS
OR
VEB
3/3,14/3-dihydroxy-5/3-20(22)-cardenol ide
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide 3-aceta te
3/3,14/3-dihydroxy-5/3,17a-20(22)-cardenolide
3/3,12/3,14/3-trihydroxy-5/3-20(22) cardenol ide
3/3,14/3,16/3-trihydroxy-5/3-20(22) -cardenolide
3/3,14/3,16/3-trihydroxy 5/3-20(22)-cardenolide 3-ace ta te
3/3,14/3,16/3-trihydroxy-5/3-20(22)-cardenolide 16-aceta te
3/3,14/3,16/3-trihydroxy-5/3-20(22) cardenol ide 3 ,16-d iace ta te
1 Ία, 20/3, 21 - tr ihydroxy -4 -p r eg -n e n e - 3 , l l - d i o n e
17a, 21 -dihydroxy -4-pregnene -3 ,11 ,20 - t r i one
17a, 21 -d ihydroxy-1 ,4 -p regna -d i e n e - 3 , 1 1 , 2 0 - t r i o n e
5a -pregnane-3 ,20-d ione
5/3-pregnane-3,20-dione
l l a - h y d r o x y - 5 a - p r e g n a n e - 3 , 2 0 -dione
3/3-OH—3-C=0
12/3-OH
3/3-OH—3-C=0; 12/3-OH
3/3-OAc-+3-C=0 12/3-OH
3 / 3 - O H ^ 3 - 0 0
3 / 3 - O H - > 3 - 0 0
3 /3-OH^3-C=0
3/3-OAc->3-C=0
3ß-OH->3-C=0
3/3-OAc-3|3-OH; 16/3-OAc^l6/3-OH 3/3-OAc->3-C=0; 16/3-OAc—16/3-OH
3/3-OAc-*3-C=0
3j3-OAc-*3/3-OH
20-C=O-20/3-OHJ (limited oxygen)
Δ - 2 0 - C = O -20/3-ΟΗ (normal a e r a -tion)
20-C=O — 20β-ΟΗ
12/3,15a-diOH
12/3,15α-diOH
1 5 Ö - O H
N-677
N-677
N-677
N-677
N-681
N-677
N-677
N-677
N-677
N-677
N-677
N-677
N-677
S-951
S-951
S-951
S-951
S-951
S-816
S-816
S-816
1
Δ
1
Δ
334
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: CALONECTRIA CANDELOSPORA
CANDIDA (Imperf. - Moniliales) (Imperf. - Moniliales)
SPECIES
decora
CANDELOSPORA
penicil loides
CANDIDA
guill iermondii
SOURCE
VEB
FRI
NRRL
SUBSTRATE
l l a -hydroxy-5 /3 -pregnane-3 ,20-dione
3a, 6a -dihydr oxy -5/3 -pr egnan -20-one
3/3-hydroxy -5 -pr egnene - 3 , 2 0 -dione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione (11α,12α-3Η2)
9ö-hydroxy-4 -p regnene-3 ,20-dione
l l a , - hyd roxy-4 -p regnene -3 ,20 -dione
11/3-hydroxy -4 -pr egnene -3 ,20 -dione
12«-hydroxy-4-pregnene-3 ,20-dione
14a-hydroxy-4-pregnene-3 ,20-dione
15/3-hydroxy -4 -pregnene - 3 , 2 0 -dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
4 -p regnene -3 ,11 ,20 - t r i one
17a, 21-dihydroxy-4-pregnene -3,20-dione
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
REACTION
15a -OH
11a-OH
3 ß - O H - 3 - C = 0 ; Δ 5 - Δ 4 ; 12/3,15α-diOH
12/3,15a-diOH
12|3,15a-diOH
(o218)
12/3,15a-diOH
15a-OH
15a-OH
15a-OH
15a-OH; 12a-O H - 1 2 - C = 0
12/3-OH
12/3-OH
15a-OH
15a-OH
11a-OH
-
-
REF.
S-816
S-812
S-816
S-814
K-485
H-370
S-810
S-814
S-817
S-810
S-810
S-814
S-810
S-810
S-849
M-587
M-587
M-587
335
TABLE I I I TAXONOMY
Transformat ions by Genus: CANDIDA
CANTHARELLUS CARPENTELES
CATENABACTERIUM
(Basidio. - Agaricales) (Asco. - Eurotiales) (Schizo. - Eubacteriales)
SPECIES
kruse i
pu lche r r ima
util is
CANTHARELLUS
cibar ius
CARPENTELES
javanicus
CATENABACTERIUM
catenaforme
1 *
1 *
SOURCE
NRRL
IFO(C964)
NRRL
NRRL
FRI
NG
SUBSTRATE
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
1 la, 21 -dihydr oxy -4 -pr egnene -3,20-dione
17a, 21-dihydr o x y - 1 , 4 - p r e g n a -d iene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
5-cholesten-3/3-ol
4-choles ten-3-one
3/3-hydroxy-5-pregnen-20-one
3/3,1 la -dihydroxy -5 -pregnen-20-one
21 -hydroxy-4 -p regnene -3 ,20 -dione
11/3,17a, 21 - t r ihydroxy -4 - p r e g -nene -3 ,20-dione
17a, 21-dihydr oxy-4-pregnene-3 ,11 ,20 - t r ione
17a, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r ione 21-aceta te
REACTION
—
-
-
2 0 - C = O -20/3-OH
2 0 - C = O ^ 20/3-OH
-
-
-
-
11a-OH
— (anaerobic)
— (anaerobic)
— (anaerobic)
— (anaerobic)
— (anaerobic)
3-C=0^3/3-OH; Δ4-+5α-Η
(anaerobic)
3 -C=0-3 /3 -OH; Δ 4 ^ 5 α - Η
(anaerobic)
— (anaerobic)
REF.
M-587
M-587
M-587
T-958
T-958
M-587
M-587
M-587
R-778
S-849
T-973
T-973
T-973
T-973
T-973
P-739 ; T-973
P-739 ; T-973
T-973
336
Transformat ions by Genus:
TABLE I I I
CELLULOMONAS CEPHALOSPORIUM
TAXONOMY
(Schizo. - Eubacter ia les) (Imperf. - Moniliales)
SPECIES SOURCE SUBSTRATE REACTION
CELLULOMONAS
biazotea NRRL
CEPHALOSPORIUM
acremonium NRRL-3092
SarsasapogenH
Diosgenin
4 -dehydrotigogeione
4 - e s t r e n - 3 - o n e
4-andr os tene-3 ,17-d ione
17a-oxa-D-homo - 1 , 4 - a n d r o s t a -d iene-3 ,17-dione
4-pregnene-3 ,20-d ione (with and without 4-C14)
16-C=0; (v ia 16a OH and 16/3-OH)
16a-OH — 16-C=0
16/3-OH -> 16-C = 0
16a-OH
16/3-OH
1 6 - C = 0 -> 16ß-OH
16α-OH -16/3-OH ( via 16-C = 0)
1 7 - C = 0 -13 ,17 - seco -13a-OH-16-COOH
1 7 - C = 0 — 17a-o x a - 1 7 - C = 0
17a-oxa-17-C = 0 - 1 7 , 1 7 a -seco-13q-OH-16-COOH
17ß-Ac-17/3-OH
17j3-Ac—13,17-seco-13q-OH-16-COOH
17|3-Ac->17-c=o
17/3-Ac—17a-oxa-17-C = 0
M-587
M-587
M-587
S-793a
S-793a
S-793a
S-793a
S-793a
S-793a
S-793a
H-398
H-398
H-398
H-398
H-398
H-398
H-398
R E F .
337
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: CEPHALOSPORIUM CEPHALOTHECIUM (Imperf. - Moniliales)
SPECIES
aspe rum
species
subver t ic i l la tum
CEPHALOTHECIUM (See Trichothecium)
1 roseum (Trichothecium
1 ro seum - NRRL-1665)
SOURCE
LED
LED (Z-164)
NRRL-1866
PIRI
ATCC-8685
SUBSTRATE
17a, 21 -dihydr oxy -4 -pr egnene -3,20-dione
17a, 21-dihydroxy-4-pr egnene-3,20-dione
4 -pregnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
9a - f luoro - l l /3 -hydroxy-4-p reg-nene-3 ,20-d ione
11/3,21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-dihydr oxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -9/3,11/3-oxido-4-pregnene-3 ,20-d ione
9a -fluor o -11 ß, 21 -dihydr oxy -4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
11/3-hydroxy -4 -pregnene - 3 , 2 0 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione aceta te
11/3,21 -dihydroxy -4 -pregnene -3 ,20-dione
REACTION
7/3-OH
7/3-OH
7/3-OH
7/3-OH
7/3-OH
7/3-OH
7/3-OH
7/3-OH
7/3-OH
1 7 / 3 - A C - 1 7 - 0 0
17/3-Ac— 17a-o x a - 1 7 - C = 0
17a-OH (0218)
17a-OH; 11a, 17a-diOH
17a-OH
6/3,17a-diOH
l l a , 1 7 a - d i O H
6/3,17a-diOH; 21-OAc—21-OH
l l a , 1 7 a - d i O H ; 21-OAc—21-OH
17a-OH;l l /3-OH -+n-c=o
17a-OH
R E F .
B-56
B-55
B-56
B-56
B-56
B-56
B-56
B-56
B-56
B-67
B-67
H-374
M-581; M-600
M-600
M-581
M-581
M-600
M-600
M-581; M-600
M-600
338
T r a n s f o r m a t i o n s by G e n u s :
TABLE I I I
CEPHALOTHECIUM CERATOSTOMELLA
CERCOSPORA
TAXONOMY
(Asco. - Sphaeriales) (Imperf. - Moniliales)
SPECIES
roseum
CERATOSTOMELLA
fimbriate (fimbriata)
CERCOSPORA (See genus Cercosporina)
apii
baticola
beticola
calotropidis
canescens
chenopodii
c ladosporioides
cru enta
diazu
SOURCE
ATCC-8685
FAHU
IFO (6161)
FAKU
IFO (6162)
KAG (C-32)
KAG (C-33)
CBS
IFO (6163)
CBS
CBS
IFO (6164)
CBS
SUBSTRATE
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
4 -p regnene -3 ,11 ,20 - t r i one
21 -hydroxy-4 -p regnene -3 ,11 ,20 -tr ione
17ö, 21 -dihydroxy -4 -p regnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
REACTION
11a-OH
17a-OH
17a-OH
-
oxidation -products not identified
-
-
-
-
oxidation -p roduc t s not identified
oxidation -products not identified
oxidation -products not identified
oxidation -p roduc t s not identified
oxidation -products not identified
oxidation -products not identified
R E F .
M-600
M-600
M-581; M-600
S-849
K-472
S-849
K-472
K-472
K-472
K-472
K-472
K-472
K-472
K-472
K-472
TABLE I I I
Transformat ions by Genus: CERCOSPORA
339
SPECIES
fusca
hibsci-cannabini
i tal ica
kaki
kikuchii (see genus Ce rcospo r -
ina)
lagenarium
macrospora
1 malvacearum
medicaginis
melongenae
melonis
SOURCE
CBS
KAG
CBS
CBS
FRI
NARI
TNAES
CBS
CBS
CBS
KAG(C-36)
CBS
SUBSTRATE
17a,21-dihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17«, 21 -d ihydroxy-4-pregnene-3,20-dione
17a,21 -dihydr oxy -4 -pregnene -3,20-dione
17a, 21-dihydr oxy-4-p regnene-3 ,20-d ione
17o,21 -d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydr oxy -4 -pregnene -3,20-dione
17a, 21-dihydr oxy-4-pregnene-3,20-dione
17a, 21 -dihydr oxy -4 -pregnene -3,20-dione
17a, 21-dihydr oxy-4-pregnene-3,20-dione
17a, 21-dihydr oxy-4-pregnene-3,20-dione
4 -andros tene-3 ,17-d ione
9a -hyd roxy -4 -and ros t ene -3 ,17 -dione
12a-hydroxy-4-andros tene -3,17-dione
14a-hydroxy-4-andros tene-3,17-dione
REACTION
oxidation -products not identified
oxidation -products not identified
oxidation -products not identified
oxidation -products not identified
-
-
oxidation-products not identified
oxidation -products not identified
-
11a-OH
9a,12a-diOH
9a,14a-diOH
9a,15/3-diOH
9a,18-diOH
12a-OH
14a-OH
15/3-OH
18-OH
9a-OH
9a-OH
R E F .
K-472
K-472
K-472
K-472
S-849
S-849
S-849
K-472
K-472
K-472
K-472
K-473
K-473
K-473
K-473
K-473
K-473
K-473
K-473
K-473
K-473
340
TABLE I I I
T r a n s f o r m a t i o n s by G e n u s : CERCOSPORA
SPECIES
melonis
musae
musa rum
nicotianae
oryzae
ros icola
sc i rpicola
s e sami
taiwanensis
vaginae
violae
zebrina
zinniae
SOURCE
CBS
CBS
CBS
CBS
CBS
FRI
NAH
CBS
CBS
IFO(6165)
CBS
CBS
CBS
CBS
KAG
SUBSTRATE
15/3 -hydr oxy -4 -androstene -3,17-dione
1 la, 21 -dihydr oxy -4 -pr egnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17α, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-dihydr oxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-dihydr oxy-4-pregnene-3,20-dione
17a, 21-dihydr oxy-4-pregnene-3,20-dione
17a, 21 -dihydr oxy -4 -pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene-3,20-dione
17a, 21-dihydr oxy-4-pregnene-3,20-dione
REACTION
9a-OH
8j3-OH;15j3-OH
-
-
oxidation -products not identified
-
l i a - O H
-
-
l i a - O H
X-OH; Δ4 — 5ξ-Η
-
oxidation -products not identified
oxidation -products not identified
-
-
11a-OH
11/3-OH
R E F .
K-473
K-472; K-473
K-472
K-472
K-472
K-472
S-849
S-849
K-472
K-472
K-472
K-472
K-472
K-472
K-472
K-472
K-472
K-472
341
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: CERCOSPORELLA CERCOSPORINA CHAETOCLADIUM CHAETOMELLA
(Imperf. - Moniliales) (Imperf. - Moniliales) (Phyco. - Mucorales) (Imperf. - Sphaeropsidales)
SPECIES
CERCOSPORELLA herpotr ichoides
CERCOSPORINA
(see genus Cercospora)
CHAETOCLADIUM
1 brefeldii
CHAETOMELLA
1 oblonga
SOURCE
ATCC-12083
FRI
SSSR
ATCC-12718
SUBSTRATE
4-pregnene-3 ,20-d ione
11/3,12ß-oxido-4-pregnene - 3 , 2 0 -dione
9a - f l uo ro -4 -p regnene -3 ,11 ,20 -t r ione
12a -methyl -4 -pr egnene - 3 , 1 1 , 20- t r ione
4 ,16-pregnad iene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4 -andr ostene -3 ,17 -dione
17ß-hydroxy-4-andros ten-3-one
20-hydroxy-5a-pregnan-3-one
20-hydroxy-5i3-pregnan-3-one
4 -pregnene-3 ,20-d ione
17a-hydroxy-4-p regnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
6ß- f luoro-17a-hydroxy-4-preg-nene-3 ,20-d ione
6a -fluoro -17a, 21 -dihydr oxy -16 -méthylène -4 -pregnene - 3 , 2 0 -dione
REACTION
21-OH
21-OH
21-OH
21-OH
21-OH
-
6/3-OH
l l ß - O H
l l ß - O H
11/3-OH
11/3-OH
11/3-OH
11/3-OH
l l ß - O H
11/3-OH
l l ß - O H
l l ß - O H
R E F .
L-490
L-490
L-490
L-490
L-490
S-849
E-224
S-789
S-789
S-789
S-789
S-789
S-789
S-789
S-789
H-391
A-7
kikuchii
342
TABLE I I I TAXONOMY
Transformat ions by Genus: CHAETOMELLA CHAETOMIUM (Asco. - Sphaeriales)
SPECIES SOURCE SUBSTRATE REACTION REF.
oblonga
raphigera
ATCC-12718
ATCC-12719
CHAETOMIUM
cochloides NG
funicolum
QM-624
QM-33C
17a, 21 -d ihydroxy-1 ,4 -pregna-diene - 3 , 20-dione
4 ,6 -pregnadiene -3 ,20-dione
4 -andros tene-3 ,17-d ione
17/3-hydroxy-4-androsten-3-one
20-hydroxy-5a-pregnan-3-one
20-hydroxy-5i3-pregnan-3-one
4-pregnene-3 ,20-d ione
17a-hydroxy-4-pregnene-3 ,20-dione
17α, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-d ihydroxy-1 ,4 -pregna-d iene-3 ,20-d ione
4 ,6 -p regnad iene-3 ,20-d ione
5-cholesten-3/3-01 (sole carbon source)
24 -me thy l -5 ,7 ,22 -cho l e s t a t r i en -3/S-ol (sole carbon source)
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - l , 4 -pregnadiene-3 ,20-d ione
17a-hydroxy-1 ,4-pregnadiene -20-one
17a, 21-d ihydroxy-1 ,4 -pregna-d iene-3 ,20-d ione
1 1/3 -fluor o- 17α, 21 -dihydroxy -9α- iodo-16α-methy l -1 ,4 -pregnadiene -3 ,20-dione
l l /3- f luoro-17a ,21-dihydroxy-9a-iodo-16/3-methyl - l ,4 -pregna-d iene-3 ,20-d ione
17a, 21-d ihydroxy-1 ,4 -pregna-diene -3 , 11 ,20 - t r iene
17a, 21 -dihydroxy -16a - methyl -1,4 -pregnadiene - 3 , 1 1 , 2 0 -t r ione
11/3-OH
utilization
utilization
3-OH
6/3-OH
3-OH
6/3-OH
6/3-OH
3-OH
6/3-OH
S-789
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
S-789
S-789
S-789
S-789
S-789
S-789
S-789
S-789
S-789
S-789
S-793c
S-793c
C-108
C-108
C-108
N-691
N-691
C-108
N-690; N-692
343
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by G e n u s :
CHAETOMIUM CHALARA
CHLORELLA CHOANEPHORA
CHROMOBACTERIUM
(Imperf. - Maniliales) (Chlorophyta - Chlorococcales) (Phyco. - Mucorales) (Schizo. - Eubacter ia les)
SPECIES
globosum
species
succineum
CHALARA
my coder ma
CHLORELLA (Algae)
1 pyrenoidosa
species
CHOANEPHORA
1 cucurbi ta rum
CHROMOBACTERIUM
1 violaceum
SOURCE
FRI
wise
NRRL
QM(1044)
FRI
UM(C-37-2)
NG
SSSR
NG
SUBSTRATE
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
3/3,5/3,14/3-trihydroxy-19-oxo-20(22)-cardenolide
plant saponins
17a -hydroxy- l , 4 -p regnad iene -3,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
3/3 -hydroxy - 5 -androsten -17 -one
4 -andros tene-3 ,17-d ione
4 -pregnene-3 ,20-d ione
5-cholesten-3/3-01
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
5 -cholesten -3/3-ol (sole carbon source)
REACTION
Δ1; l l a - O H
3/3-OH-»3-C=0; 5/3-OH—Δ4
-6/3-OH
-
reduction to 4 products
1 7 - C = 0 -17/3-OH
toxic (but cul ture could be adapted to sub -s t ra te )
-20-C=O -» 20ß-OH
11α-OH; 11/3-OH; 6/3-OH
R E F .
S-849
S-891
K-478
C-108
S-849
G-321
G-321
G-321; G-322
G-321
V-1045
E-224
T-1030
344
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: CIRCINELLA CLADOSARUM
CLADOSPORIUM
(Phyco. - Mucorales) (Imperf. - Moniliales) (Imperf. - Moniliales)
SPECIES
muscae
s implex
spec ies
sydowi
umbel lata
CLADOSARUM
olivaceus (olivaceum)
CLADOSPORIUM
cladospor iodes
fulvam (fulvum)
he rba rum
SOURCE
VEB
SSSR
NRRL
VEB
FRI
NRRL
FRI
NRRL
TNAES (S-10-1)
FRI
SUBSTRATE
17/3-hydroxy-4-androsten-3-one
9a, 17/3-dihydroxy-4-androsten-3-one
17a ,21-d ihydroxy-4-pregnene-3,20-dione
Saponins (sapogenin - glycosides)
4 -pregnene-3 ,20-d ione
dione
14a-hydroxy-4-p regnene-3 ,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
17a ,21-d ihydroxy-4-pregnene-3,20-dione
Saponins (sapogenin - glycosides)
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
REACTION
9a-OH
9a-OH; 17/3-OH -» 1 7 - C = 0
17/3-OH -1 7 - C = 0
6/3-OH;lla-OH; 11/3-OH
-
9a-OH
14a-OH
9a,14a-diOH
14a-OH
9a-OH
6j3-OH
-
-
-
11a-OH
hydrolysis of glycosides to aglycones
-
REF.
R-748
R-748
R-748
E-224
K-478
S-815
S-815
S-815
S-815
S-815
S-849
M-587
M-587
M-587
S-849
K-478
S-849
S-849
9α-hydroxy-4-pregnene-3,20-
TABLE I I I
Transformat ions by Genus: CLADOSPORIUM
345
SPECIES
he rba rum
res inae
SOURCE
NRRL
CBS
NRRL 2778
SUBSTRATE
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
17ß-hydroxy-4-andros ten-3-one
4 -p regnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
6a - f luoro-4-pregnene-3 ,20 -dione
6/3-fluoro-4-pr egnene -3 ,20 -dione
1 l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
l l ß - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
6 a - m e t h y l - 4 - p r e g n e n e - 3 , 2 0 -dione
6/3- methyl -4 -pregnene - 3 , 2 0 -dione
6 a - f l u o r o - l i a - h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
6/3-fluoro-1 la -hydroxy -4 - p r e g -nene-3 ,20-d ione
6 a - f l u o r o - l l ß - h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
6/3-fluoro- l l ß -hydroxy -4 - p r e g -nene -3 ,20 -dione
6a -methyl -1 l a -hydroxy -4 - p r e g -nene-3 ,20-d ione
6ß -methyl - l i a -hydroxy -4 - p r e g -nene -3 ,20 -dione
6 a - m e t h y l - l l ß - h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
REACTION
—
-
-
17ß-OH -» 1 7 - C = 0
17ß-Ac — 1 7 - C = 0
17ß-Ac -17ß-OH
17ß-Ac — 17ß-OAc
17ß-Ac — 17ß-OAc
17ß-Ac -17ß-OAc
17ß-Ac — 17ß-OAc
17ß-Ac — 17ß-OAc
17ß-Ac — 17ß-OAc
17ß-Ac -> 17ß-OAc
17ß-Ac -17ß-OAc
17ß-Ac — 17ß-OAc
17ß-Ac -17ß-OAc
17ß-Ac -» 17/3-OAc
17ß-Ac — 17ß-OAc
17ß-Ac — 17ß-OAc
17ß-Ac -17ß-OAc
17ß-Ac -» 17ß-OAc
R E F .
M-587
M-587
M-587
F-254
F-254
F-254
F-254
F-250
F-250
F-250
F-250
F-250
F-250
F-250
F-250
F-250
F-250
F-250
F-250
F-250
F-250
346
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by G e n u s : CLADOSPORIUM
CL AVARIA CLAVICEPS
CLITOCYBE
(Basidio. - Agaricales) (Asco. - Eypocreales) (Basidio. - Agaricales)
SPECIES
res inae
spec ies
CLAVARIA
mucida
CLAVICEPS
purpurea
CLITOCYBE
adirondackensis
ciavipes
odor a
[ species "C"
SOURCE
NRRL-2778
ATCC-13026
MCC(SF-52$
FRI
NG
AL(SS-43)
AL(G-107)
AL(H-21)
AL(G-8)
SUBSTRATE
6/3-methyl-l l /3-hydroxy-4-pregnene-3 ,20-d ione
4 -p regnene -3 ,11 ,20 - t r i one
6ö- f Iuoro -4 -p regnene-3 ,11 ,20-t r ione
6 j3-f luoro-4-pregnene-3 ,11,20-t r ione
6a -methy l -4 -p r e g n e n e - 3 , 1 1 , 20- t r ione
6 ß - m e t h y l - 4 - p r e g n e n e - 3 , 1 1 , 20- t r ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
21-hydroxy-4-p regnene-3 ,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
3/3, 6/3, 8/3,14/3-tetrahydroxy-4,20,22 -bufatrienolide 6-aceta te 3-glucoside
3/3,14/3-dihydroxy-5/3-20(22)-cardenol ide-3- [g lucosyl -digitoxosy 1 -digitoxosy 1 -digitoxoside]
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
REACTION
17/3-Ac-17/3-OAc
17/3-Ac-17/3-OAc
17/3-Ac-17/3-OAc
17/3-Ac-17/3-OAc
17/3-Ac-17/3-OAc
17/3-Ac 17/3-OAc
1ξ-ΟΗ
7/3-OH
7/3-OK
7/3-OH
6/3-OH;llö-OH
3ß-[l\-gbicosiae] - 3/3-OH
glucosyl-digitoxosyl-digitoxosyl-digitoxoside — digitoxosyl-digitoxosyl-digitoxoside
-
-
-
-
REF.
F-250
F-250
F-250
F-250
F-250
F-250
S-941
S-941
M-570
M-570
S-849
S-936a
S-936a
S-825
S-825
S-825
S-825 J
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by G e n u S : CLOSTRIDIUM (Schizo.-Eubacteriales)
347
SPECIES
bifermentans
paraputrificum
1 perfringens
sporogenes
tertium
SOURCE
IMJ
IMJ
NG
IMJ
NG
IMJ
SUBSTRATE
3/3-hydroxy-5-androsten-17-one
4 -androstene -3,17 -dione
3a-hydroxy-5a-androstan-17-one
3ß-hydroxy-5-androsten-17-one
17/3 -hydr oxy -4 -andr osten - 3 -one
4-androstene-3,17-dione
l,4-androstadiene-3,17-dione
4-pregnene-3,20-dione
21-hydroxy-4-pregnene-3,20-dione
21-hydroxy-4-pregnene-3,20-dione acetate
17a, 21 -dihydroxy-4-pregnene-3,11,20-trione
17a, 21 -dihydroxy -4 -pr egnene -3,11,20-trione 21-acetate
3α, 7α, 12a-trihydroxy-5/3-cholanic acid
3/3-hydroxy -4 -andr osten-17-one
4-androstene-3,17-dione
5-cholesten-3/3-ol
17/3-hydr oxy-4-andr osten-3-one
4-pregnene-3,20-dione
21-hydroxy-4-pregnene-3,20-dione
21-hydroxy-4-pregnene-3,20-dione acetate
REACTION
-
-
-
Δ4-5/3-Η; 3-C=0^3a-OH
Δ^5β-Η; 3-C=0->3a-OH
Δ4^5β-Η
Δ ^ Η ; Δ4 - 5/3-H
l 4
Δ — H; Δ — 5/3-H; 3-C=0 —3a-OH
3-C=0— 3a-OH; Δ4 - 5/3-H
3-C=0-3a-OH; Δ4->5/3-Η
3-C=0-3a-OH; Δ4^5/3-Η
3-C=0^3a-OH; Δ4-5/3-Η
3-C=0->3a-OH; Δ4-5/3-Η
7a-OH—7-C=0
-
-
-
Δ4-5/3; 3-C=0-3a-OH
3-C=0-3a-OH; Δ4-+5/3-Η
3-C=0-3a-OH; Δ4-5/3-Η
3-C=0-»3a-OH; Δ4^5β-Η
REF.
S-822
S-822
S-822
S-822
S-823
S-822
S-824
S-824
S-824
S-823
S-823
S-823
S-823
S-823
N-675
S-822
S-822
S-914
S-823
S-823
S-823
S-823
348
T A B L E I I I TAXONOMY
Transformations by Genus: £ L ° J ™ D I U M
J COCHLIOBOLUS COKEROMYCES
COLLETOTRICHUM
(Asco. - Sphaeriales) (Phyco, - Mucoraies) (Imperf. - Melanconiales)
SPECIES
te r t ium
welchii
COCHLIOBOLUS
miyabeanus
COKEROMYCES
recurva tus
COLLETOTRICHUM
ant i r rh in i
de r r i d i s
gloeosporioides
linde muthianum
SOURCE
IMJ
NG
FAKU
FRI
CBS
Cornell (Plant P a t h -ology Dept0 )
CBS
TNAES
ATCC-12611
SUBSTRATE
1Ία,21 -d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione
17a,21 -d ihydroxy-4-pregnene-3 ,11 ,20- t r ione 21-acetate
5~cholesten-3/3-oi
1Ία,21 -d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -p regnene-3,20-dione
20/3-hydr oxy - A-nor - 5a -p reg -nan-2-one
A-nor -5a -p regnane-2 ,20-d ione
A-nor -3 -p regnene-2 ,20-d ione
4-pregnene-3 ,20-d ione
17/3-hydr oxy-4 -es t r en-3-one
17a ,21-d ihydroxy-4-pregnene-3,20-dione
pregnane-3 ,20-d ione
4-pregnene-3 ,20-d ione
l l ß , 17a-d ihydroxy-18-nor-4-pregnene-3 ,20-d ione
9a-f luoro- l l /3 ,17a-dihydroxy-16a-methy l -1 ,4 -pregnad iene-3,20-dione
REACTION
3 - C = 0 - 3 a - O H ; Δ4-5/3-Η
3-C = 0 - 3 a - O H ; Δ4-5/3-Η
-
-
6/3-OH;lla-OH
17/3-Ac-17j3-OH; 5a-H -» 5a-OH
5a-H -» 5a-OH
6/3-OH
15a-OH
12/3-OH
12/3-OH; 17/3-OH -*17-C=0
11a-OH
21-OH unspecified products
21-OH unspecified products
21-OH
21-OH
R E F .
S-823
S-823
S-914
S-849
S-849
P-706a
P-706a
L-503a
F-285; F-287; F-288
D-152
D-152
S-849
H-324
H-324
A-12
M-598
TABLE I I I
Transformat ions by Genus: COLLETOTRICHUM
COLLYBIA
TAXONOMY
(Basidio. - Agaricales)
349
SPECIES
lindemothianum
phomoides *
*
pisi
1 species
COLLYBIA
dryophila
SOURCE
ATCC-12611
IAM
ATCC-12521
NARI
NG
OR
ATCC-12520
IAM
AL
SUBSTRATE
17a -hyd roxy - l , 4 -p r egnad i ene -3 ,11 ,20 - t r ione
17a -hydroxy-18-nor -4 -p regnene-3 ,11 ,20 - t r i one
1 la -hydroxy-16a- methyl -18 -nor -4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
17a, 21-dihydroxy-4-pregnene -3,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4,9(11) -pregnadiene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
6a-f luoro-16a, 17a, 21 - tr ihydroxy-4-pregnene-3 ,20-d ione 16 ,17 -acetonide
6a-f luoro-16a, 17a, 21- t r ihydroxy-4-pregnene-3 ,20-d ione 16 ,17 -cyclohexanonide
17a-a l ly l -17/3-hydroxy-4-es t ren-3-one
21-hydroxy-4 -p regnene-3 , 20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
4 -p regnene-3 ,20-d ione
REACTION
21-OH
21-OH
21-OH
-
11/3-OH
11/3-OH; l i a - O H
6/3,12a-diOH
6/3,X-diOH
9(11)
Δ —9j3,11/3-oxide; 6/3,12a-diOH
l i a - O H
l i a - O H
l l a - O H
16/3-OH
11/3-OH
l l a - O H ; 11^-OH
—
17/3-Ac^l7a-o x a - 1 7 - C = 0
R E F .
H-324
A-10; A-13
A - l l
S-849
T-1003
T-1003
F-277; F-279
F-277; F-279
F-277; F-279; F-280
S-849
D-159
D-159
S-950
T-1004
T-1004
S-849
S-825
350
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: COLLYBIA
CONIDIOBOLUS CONIOTHYRIUM
(Phyco. - Entomophthorales) (Imperf. - Sphaeropsidales)
SPECIES
velutipes
CONIDIOBOLUS
species
CONIOTHYRIUM
hel lebori
helleborine
SOURCE
FRI
NRRL
NRRL-1612
TNAES
SAG (078)
SQ ( mutant)
ATCC-12522
SUBSTRATE
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
17a, 21-dihydroxy-4-pregnene -3,20-dione
1 la, 21 -dihydroxy - 4 -pre gnene -3 ,20-dione
4-pregnene-3 ,20-d ione
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a-oxa-D-homo-4-andros tene -3,17-dione
21-hydroxy-4-p regnene-3 ,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
REACTION
-
-
-
-
2/3-OH
11α-OH
11α-OH
11/3-OH
12/3-OH
6β-ΟΗ
11/3-OH
12/3-OH
11/3-OH
6/3-OH
7a-OH
l l a - O H
11/3-OH
l l a - O H
l l ß - O H
REF.
S-849
M-587
M-587
M-587
W-1073
W-1073
S-849
R-749
R-749
R-749
R-749
R-749
T-993
F-281 ; F-282; T-994
F-281 ; F-282; T-994
T-1003; T-1004
T-1003; T-1004
T-1003; T-1004
F-288; R-749; T-993; T-1003; T-1004
351
T r a n s f o r m a t i o n s by G e n u s :
TABLE I I I CONIOTHYRIUM
CONOCYBE COPRINUS
CORDYCEPS CORETHROPSIS
CORIOLUS
TAXONOMY
(Basidio«, - Agaricales) (BasidiOo - Agaricales) (Asco0 - Hypocreales) (Imperfo - Moniliales) (Basidio«, - Agaricales)
SPECIES
helleborine
species
CONOCYBE
sil igenoides
COPRINUS
a t romenta r ius (a t ramentar ius)
sobil iferus
CORDYCEPS
mi l i t a r i s
CORETHROPSIS
hominis
CORIOLUS
1 vers ico lor
SOURCE
ATCC-12522
NRRL-2476
NG
AL(G-75)
AL(G-63)
FRI
FRI
ATCC-13488
SUBSTRATE
1 la, 21 -dihydroxy - 1 , 4 -pr egna -d iene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
l l / 3 -hydroxy-4 -p regnene-3 ,20-dione
17cc-hydroxy-4-pregnene-3,20-dione
11/3,1 la -dihydroxy -4 -pregnene -3,20-dione
11a, 21 -dihydroxy -4 -pregnene -3,20-dione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
REACTION
11/3-OH
21-OH
21-OH
21-OH
21-OH
11«-OH
-
—
6/3-OH; 11a-OH
-
6ß-OH
14a-OH
15/3 -OH
REF.
T-1004
D-186
D-186
D-186
D-186
C-113
S-825
S-825
S-849
S-849
B-63
B-63
B-63
352
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus : CORTICIUM (See Rhizoctonia)
(Basidio. - Agaricales)
Other Synonyms - Hypochnus and Pellicularia
SPECIES
centrifugum
centrifugus
graminum
mic rosc le ro t i a
prac t ico la
SOURCE
ATCC-11908
FAHU
FRI
NARI
CMI
NRRL-2727
CMI
SUBSTRATE
4-andros tene-3 ,17-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pr egnene -3,20-dione
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
4 -pregnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21 -d ihydroxy- l , 4 -p regna-d iene-3 ,20-d ione
4 -andros tene -3 ,17 -dione
4 -pregnene-3 ,20-d ione
21-hydroxy-4 -p regnene-3 ,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione 21-aceta te
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione 21-aceta te
4 -pregnene-3 ,20-d ione
21-hydroxy-4 -p regnene-3 ,20-dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
17a, 21 -d ihydroxy- l , 4 -p regna-d iene-3 ,20-dione
REACTION
1 6 - C = 0 ; 1 7 - C = 0 -17/3-0H
16ß-OH; 1 7 - C = 0 -» 170-OH
-
2/3-OH;6j3-OH; 11a-OH
-
11-OH
11-OH
l l a - O H ; l l / 3 - O H
11-OH
19-OH
19-OH
19-OH
l l ß - O H
l lß-OH;21-OAc - 2 1 - O H
19-OH
19-OH; 21-OAc -»21 -OH
11-OH
11-OH
11a-OH; 11/3-OH
11-OH
R E F .
D-166
D-166
S-849
S-849
S-849
H-349
H-349
H-349
H-349
H-350
H-350
H-350
H-350
H-350
H-350
H-350
H-349
H-349
H-349
H-349
TABLE I I I
353
T r a n s f o r m a t i o n s by G e n u s : CORTICIUM
SPECIES
prac t ico la
roefsi i
sa lmonicolar
sasak i i
SOURCE
NRRL-2724
FAKU
FAKU
ATCC-13269
CMI
IFO
IFO( 5254)
NG
SUBSTRATE
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21 -dihydroxy-4-pr egnene-3,20-dione
17a, 21 -d ihydroxy-1 ,4 -p regna-d iene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
17a, 21 -d ihydroxy-1 ,4 -p regna -d iene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
REACTION
l l ß - O H
-
—
l l ß - O H
l l ß - O H
l l ß - O H
1 1 - C = 0 (via l lß -OH)
11-OH
11-OH
11a-OH; 11/3-OH
11-OH
11a-OH
l l ß - O H
19-OH
6ß-OH
l i a - O H
l l ß - O H
l l ß - O H ; l l - C = 0 (via l l ß -OH)
Δ1; l l ß - O H
19-OH
19-OH
R E F .
H-350
S-849
S-849
H-350
H-350
H-350
H-350
H-349
H-349
H-349
H-349
H-347
H-347
H-347; N-660
H-327
H-325; T-954
H-325; T-954
H-327
H-327
H-325; H-326; T-954
N-672
354
T r a n s f o r m a t i o n s by Genus:
TABLE I I I
CORTICIUM CORTINARIUS
CORTINELLUS CORYNEBACTERIUM
TAXONOMY
(Basidio. - Agaricales) (BasidiOo - Agaricales) (Schizo, - Eubacteriales)
SPECIES
solani (see vagum)
spec ies
vagium
vagum (see solani)
CORTINARIUS
evernius
CORTINELLUS
shiitake
CORYNEBACTERIUM
equi (in mixed cul ture with Tr ichomonas foetus)
(in mixed cul ture with Tr ichomonas foetus)
(in mixed cul ture with Tr ichomonas foetus)
fascians
helvolum (nomen confusum -see mediolanum and Flavobacter ium helvolum)
SOURCE
IFO(6251)
IAM(B-57, B-60 ,B-64)
S
IAM
IFO(6192)
AL(C-351)
FAKU
ATCC-10146
IAM
IAM
NG
SUBSTRATE
1 Ία, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3 ,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
4-pregnene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
l l / 3 -hyd roxy -4 -e s t r ene -3 ,17 -dione
4 - e s t r e n e - 3 , 1 1 , 1 7 - t r i o n e
4 -andros tene-3 ,17-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
3j3-hydroxy-5-androsten-17-one
17a-methyl-4-andros tene-3/3 ,17ß-diol
REACTION
Δ1; 6/3-OH
-
11a-OH
11a-OH
11a-OH
11/3-OH
19-OH
Δ4—5a-H
11a-OH
1
Δ ; enol0
1
Δ ; enol.
1
Δ
—
-
3/3-OH->3-C=0; Δ 5 - Δ 4
3/3-OH—3-C=0: Δ —>Δ
R E F .
H-348
S-849
S-849
S-840
H-350
H-350
H-350
S-825
S-849
S-830
S-830
S-830
S-849
S-849
M-546
M-546
TABLE I I I
T ransformat ions by Genus: CORYNEBACTERIUM
355
SPECIES
helvolum
(nomen confusum -see mediolanum and Flavobacter ium helvolum)
hoagii
SOURCE
NG
ATCC-7005
IAM
SUBSTRATE
3j3-hydroxy-5-pregnen-20-one
11/3-hydroxy-19-nor-4-pregnene -3,20-dione
l l ß , 17a-d ihydroxy-19-nor -4-p regnene-3 ,20-d ione
l l ß , 2 1 - d i h y d r o x y - 1 9 - n o r - 4 -pregnene-3 ,20-d ione
1 9 - n o r - 4 - p r e g n e n e - 3 , 1 1 , 2 0 -t r ione
17a-hydroxy-19-nor -4 -p regnene-3 ,11 ,20 - t r ione
4 -pregnene-3 ,20-d ione
9 a - c h l o r o - l l ß - h y d r o x y - 4 -pregnene-3 ,20-d ione
9 a - b r o m o - l l ß , 2 1 - d i h y d r o x y -4-pregnene-3 ,20-d ione 21-acetate
9 a - c h l o r o - l l ß , 17a-dihydroxy-4-pregnene-3 ,20-d ione
9 a - c h l o r o - l l ß , 2 1 - d i h y d r o x y - 4 -pregnene-3 ,20-d ione
11β, 17α, 21 - t r ihydr oxy -4 - p r e g -nene -3 ,20-dione
9 a - f l u o r o - l l ß , 1 7 a , 21- t r ihydroxy-4-pregnene-3 ,20-d ione
9 a - f l u o r o - l l ß , 1 4 a , 1 5 ß , 1 7 a , 2 1 -pentahydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione 20-cycloethyleneketal
9 a - b r o m o - 4 - p r e g n e n e - 3 , 1 1 , 2 0 -t r ione
9a -ch loro-4 -pregnene - 3 , 1 1 , 2 0 -t r ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
REACTION
3 ß - O H ^ 3 - C = 0 ; Δ —»Δ
1
Δ ; enolo
1
Δ ; enol.
1
Δ ; enol.
Δ ; enol.
1
Δ ; enol.
1
Δ 1
Δ
Δ ; 21-OAc -> 21-OH
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
Δ
1
Δ
1
Δ
R E F .
M-546
H-386
H-386
H-386
H-386
H-386
F-251
H-379
N-668
H-379
N-668
N-665; N-670
N-669
N-669
F-251
H-379
H-379
S-849
356
TABLE I I I
Transformat ions by Genus: CORYNEBACTERIUM
SPECIES
mediolanum
(in mixed cul ture with Cunninghamella blakesleeana[Hß-OH])
pseudodiphtheri t icum *
*
*
simplex (see genus -Ar throbacter )
SOURCE
NG
NG
ATCC-6946
SUBSTRATE
3/3-hydroxy -5 -andros ten-17-one
5-androstene-3/3,17/3-diol
5-androstene-3/3,16a, 17/3-triol
l /3,3/3-dihydroxy-5-pregnen-20-one
3/3,21-dihydroxy-5-pregnen-20-one 21-aceta te
3 /3 ,17a,21- t r ihydroxy-5-pregnen-20-one
3/3 ,17a,21- t r ihydroxy-5-pregnen-
3/3 ,17a,21- t r ihydroxy-5-pregnen-20-one 3 ,21-diace ta te
1 ,3 ,5(10)-es t ra t r iene-3,17/3-diol
5-androstene-3/3,17/3-diol
5-choiesten-3/3-ol (sole carbon source)
A -nor -17/3-hydroxy -3 -androsten -2-one
17/3-hydroxy-4-estren-3-one
17/3-hydroxy-4-estren-3-one aceta te
REACTION
3 /3-OH-3-C=0; Δ 5 - Δ 4
3/3-OH->3-C=0; Δ 5 - Δ 4
3 /3 -OH-3-C=0; Δ5-*Δ4
3 /3 -OH-3-C=0; Δ 5 - Δ 4
3 /3 -OH-3-C=0; Δ 5 ^ Δ 4 ; 21-OAc -»21-OH
Δ5->Δ4 ; 3/3-OH ->3-C=0
Δ5-*Δ4; 3/3 -OH ->3-C=0; 21-OAc-+21-OH
Δ 5 ^ Δ 4 ; 3/3-OAc ->3-C=0; 21 -OAc-*21 -OH
17/3-OH-^17-C=0
Δ 5 - Δ 4 ; 3/3-OH ->3-C=0
Δ 5 ^ Δ 4 ; 3/3-OH ->3-C=0;17/3-OH^17-C = 0
-
9α-ΟΗ; 17/3-OH - 1 7 - C = 0
1
Δ ; enol.
Δ ; enol. 17/3-OH -» 17-C = 0
17/3-OH -» 17-C = 0
Δ*; enol
1ξ-ΟΗ
R E F .
M-591
M-591
A - l
ß - 7 7
M-541; M-544
S-920
S-920
S-920
Z-1133
Z-1133
Z-1133
T-1033
S-885
C-128; K-487; K-488
K-487; K-488
K-487; K-488
G-315; K-487; K-488
G-315; K-487
20-one 21 -acetate
TABLE I I I
T r a n s f o r m a t i o n s by Genus : CORYNEBACTERIUM
357
SPECIES SOURCE SUBSTRATE REACTION REF.
simplex (see genus -Arthrobacter)
ATCC-6946 10/3,17j3-dihydroxy-4-estren-3-one
9/3, ll/3-oxido-4-estrene-3,17-dione
9a-bromo-4-estrene -3,11,17-trione
4,7-estradiene-3,17-dione
4,6 -estradiene -3,17 -dione
5-androstene-3ß, 17/3-diol
1 la - methyl -16 - méthylène - 5 -androstene-3/3,17/3-diol
3/3 -hydroxy -5 -andr osten -17 -one
17/3-hydroxy-4-androsten-3-one
17a-bromethinyl-17/3-hydroxy-4-androsten-3-one acetate
1 la -chlor ethinyl-17/3 -hydroxy -4-androsten-3-one acetate
1 la -ethinyl- 17/3-hydroxy -4 -androsten-3-one
17a-ethyl-17/3-hydroxy-4-androsten-3-one
Δ ; enol, D-150
1
Δ ; enol.
1
Δ ; enol.
1
Δ ; enol.
1
Δ ; enol. 1 5 4
Δ ; Δ ->Δ ; 3/3-OH-3-C;
3/3-OH->3-C= Δ 5 - Δ 4 ; 17/3-- 1 7 - C = 0
= 0
= 0 ; OH
Δ ; 3/3-OH -» 3-C = 0 ; 17/3-OH ^ 7 - Ç = 0 ; Δ ^ Δ
1 5 4
Δ ; Δ ->Δ ; 3/3-OH-»3-C=
3ß-OH-»3-C= Δ 5 - Δ 4
Δ1
17/3-OH — 1 7 - C = 0
Δ1; 17/3-OH 1 7 - C = 0
1
Δ
1
Δ
1
Δ
1
Δ
= 0
= 0 ;
R-762
R-762
B-72; Z-1126; Z-1127
Ζ_-Λ127
C-128; N-665; N-670
C-128
C-128; N-665
B-76
C-128; N-665; N-670
C-128; N-665; N-670;
. S-890
C-128
C-128; N-665
0 -694 ; 0 -695
0 -694 ; 0 -695
N-665; N-670
N-677a
358
TABLE I I I
T ransformat ions by Genus: CORYNEBACTERIUM
SPECIES
simplex (See genus -Ar throbacter )
SOURCE
ATCC-6946
SUBSTRATE
2/3,17/3-dihydroxy-4-androsten-3-one diacetate
17/3-hy dr oxy -17a - methy I - 4 andros ten-3-one
17a-bromethinyl-6a-chloro-17/3-hydroxy-4-andros ten-3-one aceta te
17a-bromethinyl-6a-f luoro-17/3-hydroxy-4-andros ten-3-one aceta te
6o -chlor o- 17α -chlor ethinyl-17/3-hydr oxy -4 -andr osten -3 - one aceta te
17α-chlor ethiny I-6α-fluor 0-17/3-hydr oxy-4-andr os ten-3-one aceta te
17α-ethyl-11/3,17/3-dihydroxy-4-andros ten-3-one
12a-fluoro-l l /3,17/3-dihydroxy-4-andros ten-3-one
11/3,17/3-dihydroxy-17α-me thy!-4 -andros ten-3-one
17/3-hydroxy-17a-methyl-16-methylene-4-andros ten-3-one
9a, l l /3-dichloro-17/3-hydroxy-17a-methyl -4-andros ten-3-one
9a -b romo-17a-e th iny l - l l /3 , 17/3-dihy dr oxy -16a - me thy 1 - 4 -andr os ten-3-one
9a-chIoro-17a-ethinyl- l l /3 ,17/3-d ihydroxy-16a-methyl -4-andros ten-3-one
17a- ethiny 1- 16a -ethyl -9a -fluor o-11/3,17/3-dihydroxy-4-andro-s ten-3-one
17a - ethiny 1-9a-fluor o -11/3,17/3-dihydroxy -16a-methyl -4 -andros ten-3-one
17a-ethinyl-16a-ethyl-17/3-hydroxy-9/3, l l ß - o x i d o - 4 -andros ten-3-one
REACTION
2/3-OAc-»2/3-OI^ 17/3-OAc — 1 7 - C = 0
1
Δ
1 LA
1
Δ
1
Δ
1
Δ
1
Δ
Δ ; 17/3-OH -» 1 7 - C = 0
1
Δ 1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
R E F .
H-399
N-665; N-667a; N-670
0 -694 ; 0 -695
0 -694 ; 0-695
0-694 ; 0 -695
0-694 ; 0 -695
N-667a
R-772
R-772
N-667a
B-76
G-308
O-701
O-701
O-701
O-701
O-701
TABLE I I I
T r a n s f o r m a t i o n s by Genus : CORYNEBACTERIUM
359
SPECIES
simplex
(in mixed cul ture with Tr ichomonas gallinae)
SOURCE
ATCC-6946
SUBSTRATE
17/3 -hydroxy -16a - methyl -1 7a -(Γ -propiny 1)-9/3,11/3-oxido-4-andros ten-3-one
17/3-hydroxy-17a-methyl-4,9(11)-andr ostadien - 3 - one
17a-bromethinyl-6-chloro-17/3-hydr oxy - 4 , 6 -andr ostadien -3-one ace ta te
17a-bromethinyl-6-f luoro-17/3-hydroxy-4 ,6 -andros tad ien-3-one aceta te
6 -chlor o - l 7α -chlor ethinyl-17/3-hydroxy-4 ,6 -andros tad ien-3-one
17a-chlorethinyl-6-f luoro-17/3-hydr oxy - 4 , 6 -andr ostadien -3-one aceta te
6a -flu oro-17/3 -hydroxy -17a -m e t h y l - 4 , 9 ( l l ) - a n d r o s t a d i e n -3-one
11/3 -hydroxy -4 -andr ostene -3 ,17-dione
9a, l l / 3 -d ich lo ro -4 -andros tene -3,17-dione
1 l a -hydroxy -16a - methyl -4 -andr os tene-3 ,17-d ione
16a -n -butyl -17a - ethinyl -17/3 -h y d r o x y - 4 - a n d r o s t e n e - 3 , 1 1 -dione
16/3-n-butyl-17a-ethinyl-17/3-h y d r o x y - 4 - a n d r o s t e n e - 3 , 1 1 -dione
17/3 -hydroxy -16a - methyl - H a -i l ' -propiny 1) -4 -andros tene -3 ,11-dione
17a - ethinyl - 9a - fluor o -17/3 -hydroxy-16a-methy l -4 -andros tene -3 ,11-d ione
17a-e th inyl -16a-e thyl -9a- f luoro-17/3 -hydroxy -4 -andros tene -3 ,11-dione
REACTION
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
REF.
O-701
G-308
0 - 6 9 4 ; 0 -695
0 -694 ; 0 -695
0 -694 ; 0 -695
0 -694 ; 0 -695
G-308
C-128; N-666; N-667
S-830
G-308
R-752
O-701
O-701
O-701
O-701
O-701
360
TABLE I I I
Transformat ions by Genus: CORYNEBACTERIUM
SPECIES
simplex (in mixed cul ture with Tr ichomonas gallinae)
SOURCE
ATCC-6946
SUBSTRATE
4 -andr ostene -3 ,11 ,17 - t r ione
16/3-methyl -4-andros tene-3 ,11 , 17-tr ione
19-nor -4 -pregnene-3 ,20-d ione
1 9 - n o r - 4 - p r e g n e n e - 3 , 1 1 , 2 0 -t r ione
11/3,21-dihydroxy-19-nor-4-pregnene-3 ,20-d ione
11/3,17q, 21- t r ihydroxy-19-nor -4-pr e gnene-3,20-dione
11/3,1 la, 21 -trihydroxy-19-nor_-4-pregnene-3 ,20-d ione 11 , 21-diacetate
21-hydroxy-19-nor -4 -p regnene-3 ,11 ,20 - t r ione
17a, 21-d ihydroxy-19-nor -4-p r e g n e n e - 3 , 1 1 , 2 0 - t r ione
17a, 21-d ihydroxy-19-nor -4-p regnene -3 ,11 ,20 - t r i one 21-aceta te
3a, 17a, 21- t r ihydroxy-5a-pregnane-11 ,20-d ione
17a, 21-dihydroxy-5a-pr egnane -3 ,11 ,20 - t r ione
17a, 21 -dihydroxy -16/3- methyl -5a -pr egnane - 3 , 1 1 , 2 0 - t r ione
17a, 21 -dihydroxy -16/3 - methyl -5a-pr egnane-3 ,11 ,20- t r ione 21-aceta te
5-pregnene-3 j3,20/3-diol
3/3,17a, 21 - t r ihydroxy-5-p reg-nene-20-one 3 ,21-diace ta te
REACTION
1
Δ
1
Δ
1
Δ ; enol.
1
Δ ; enol.
1
Δ ; enol.
1
Δ ; enol.
1
Δ ; enol.
1
Δ ; enol.
1
Δ ; enol.
1
Δ ; enol.
-
-
1 4
Δ ; Δ 1
Δ
Δ ; 21-OAc -» 21-OH
1 4
Δ ; Δ ; 21-OAc—21-OH
5 4 1
Δ - Δ ; Δ ; 3 /3 -OH-3-C=0; 20/3-OH-* 20-C=O
1 5 4
Δ ; Δ - Δ ; 3 /3 -OAc-3-C=0; 21-OAc — 21-OH
R E F .
S-830
R-752
B-71 ; B-73
B-73
H-386
H-386
H-386
H-386
H-386
H-386
C-128
C-128
K-451
K-451
K-451
K-451
C-128; N-665; N-670
C-115; C-128; N-665; N-670
TABLE I I I
T r a n s f o r m a t i o n s by Genus·. CORYNEBACTERIUM
361
SPECIES SOURCE SUBSTRATE REACTION REF.
simplex ATCC-6946 3/3,17a, 21 -trihydroxy -5 -preg-nen-20-one 3,21-diacetate
3/3-hydroxy-4-pregnen-20-one
4-pregnene-3,20-dione
4-pregnene-3,20-dione 20-cycloethyleneketal
lla-hydroxy-4-pregnene-3,20-dione
21-hydroxy-4-pregnene-3,20-dione
21-hydroxy-4-pregnene-3,20-dione acetate
9α, llß-dibromo-4-pregnene-3, 20-dione
9a-bromo-ll/3-chloro-4-pregnene -3,20-dione
9a-bromo-ll/3-fluoro-4-preg-nene-3,20-dione
9a-bromo-ll/3-hydroxy-4-preg-nene-3,20-dione
9a-chloro-ll/3-fluoro-4-preg-nene-3,20-dione
ll/3-chloro-9a-iodo-4-preg-nene-3,20-dione
3/3-OAc—3-C=0; Δ 5 -Δ 4
3/3-OAc-3-C=0;| Δ5-Δ4; Δ1; 21-OAc-21-OH
3/3-OAc^3-C=0;| Δ5-Δ4; Δ1; 20-C=O^20/3-ΟΗ; 21-OAc -21-OH
Δ1; 3/3-ΟΗ-* 3-C=0
9α-ΟΗ
Δ (ketal pre-vents degrada-tion)
Δ ; 20-C=O 20j3-OH
C-128; N-665
C-115: C-128; N-665
C-115
N-665; N-670
F-251; H-399; T-1005
P-740; S-885
F-251
T-995; T-1001
T-995
N-665; N-670
H-389: N-671
R-754
R-754
R-754
H-379
R-754
R-754 1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
362
TABLE I I I
Transformat ions by Genus: CORYNEBACTERIUM
SPECIES
simplex
SOURCE
ATCC-6946
SUBSTRATE
9a, 11/3-dichloro-4-pregnene -3,20-dione
9a-f luoro -1Iß-hydroxy-4 -p reg -nene-3 ,20-dione
l l /3 - f luoro-9a- iodo-4-pregnene-3,20-dione
11/3,21-dihydroxy-4-pr egnene -3,20-dione
16a, 21 -d ihydroxy-4-pregnene-3,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
l l /3 -hydroxy-3 ,20-d ike to-4-pregnen-18-oic acid (18 -» 11) lactone
9a -b romo- l l j 3 ,17a -d i ch lo ro -4 -pregnene-3 ,20-d ione
17a-bromo-9a , l l /3 -d ich ioro-4-pregnene-3 ,20-d ione
9 a - b r o m o - 1 7 a - c h l o r o - l l ß - f l u o r o -4-pregnene-3 ,20-dione
9a -b romo- l l j3 -ch lo ro -17a-hydroxy-4-p regnene-3 ,20-dione acetate
9a -b romo -1 1/3 -f luoro- 17a-hydroxy-4-p regnene-3 ,20-dione aceta te
9a -b romo -11/3-f luoro -6a -methyl -4-pregnene-3 ,20-d ione
9a, 17a-d ib romo- l l /3 -ch lo ro -4-p regnene -3 , 20-dione
REACTION
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
2 0 - C = O -20/3-OH
20-C=O -> 20/3-OH; Δ1
1
Δ
1
Δ
1
Δ
X
Δ
1
Δ
1
Δ
1
Δ
1
Δ
R E F .
R-754
H-379
R-754
H-389; N-665; N-670; N-671
H-376
H-389; H-399; L-522; N-665; N-671
L-522
H-389; N-665; N-670; L-522
U-1044
R-761
R-761
R-761
R-761
R-761
R-754
R-761
TABLE I I I
T ransformat ions by Genus: CORYNEBACTERIUM
363
SPECIES
simplex
SOURCE
ATCC-6946
SUBSTRATE
9a, l l /3 -d ibromo-17a-hydroxy-4-pregnene-3 ,20-d ione ace ta te
l l / 3 ,17a -d ib romo-9a - iodo-4 -pregnene-3 ,20-d ione
9a, l l / 3 -d ib romo-6a-methy l -4 -pregnene-3 ,20-d ione
9a-ch loro- l l /3 - f luoro-17a-hydroxy-4 -p regnene -3 ,20 -dione ace ta te
9a -ch lo ro - l l /3 - f luoro -6a -methy l -4 -pregnene-3 ,20-d ione
9a-chloro- l l /3-f luoro-6/3-methyl-4 -pregnene-3 ,20-d ione
l l /3 -ch loro-17a-hydroxy-9a-iodo-4-pr egnene-3,20-dione aceta te
l l /3 -ch lo ro -9a - iodo-6a-methy l -4 -p regnene-3 ,20-d ione
11/3 - chlor o-9a-iodo-6/3-methyl-4 -p regnene-3 ,20-d ione
l l j3 -ch loro-9a- iodo-17a-hydroxy-4-pregnene-3 ,20-d ione
9a, 17a-d ich loro- l l /3 - f luoro-4-p regnene-3 ,2 0-dione
9a, l l j3-dich. loro-17a-hydroxy-4-pregnene-3 ,20-d ione
9a, l l /3-d ichloro-17a-hydroxy-4-pregnene-3 ,20-d ione aceta te
9α, l l j3 -d ichloro-17a-hydroxy-4-pregnene-3 ,20-d ione caproate
9a, l l / 3 -d ich lo ro -6a -methy l -4 -pregnene-3 ,20-d ione
9a, 11/3-dichloro-6/3-methyl-4-pregnene-3 ,20-d ione
9a, 11 /3 ,17a- t r ich loro-4-preg-nene-3 ,20-d ione
9a- f luoro- l l /3 ,17a-d ihydroxy-4-pregnene-3 ,20-d ione
9a- f luoro- l l /3 ,21-d ihydroxy-4-pregnene-3 ,20-d ione
REACTION
Δ1
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
Δ1
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
R E F .
R-761
R-761
R-754
R-761
R-754
R-754
R-761
R-754
R-754
R-761
R-761
G-307
R-761
R-761
R-754
R-754
R-761
H-379· N-668
N-668
364
TABLE I I I
Transformat ions by Genus: CORYNEBACTERIUM
SPECIES
simplex
SOURCE
ATCC-6946
SUBSTRATE
1 l a , 21 -dihydroxy -1 7a -methyl -4-pregnene-3 ,20-d ione 21-aceta te
l l a , 1 7 a , 2 1 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
11/3,17a, 21- t r ihydroxy- 4 - p r e g -nene-3 ,20-d ione
(effeat of antibiotics-Ref«, B-37) (use of dr ied thalli-Ref0 F-231)
l l ß , 1 7 a , 2 1 - t r i h y d r o x y - 4 - p r e g -
11β, 17α, 21 - tr ihydroxy -4 -p reg -nene -3 ,20-dione 1 1 , 2 1 -diacetate
12/3,17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
21-(N-acetyl amino)-9a- f luoro-11/3,17a-dihydroxy-4-pr eg -nene-3 ,20-d ione
17a-bromo-9a , l l ß - d i c h l o r o -21- f luoro -4 -p regnene-3 ,20-dione
9 a - b r o m o - l l ß - c h l o r o - 2 1 - f l u o r o -17a-hydroxy-4-pregnene-3,20-dione
9a-bromo-11/3-chlor o-21-fluor o-6a -me thy l -4 -p regnene -3 ,20 -dione
9a -b romo-6a , 11/3,21 - t r i f luoro-4-pregnene-3 ,20-d ione
9 a - b r o m o - l l ß , 2 1 - d i f l u o r o - 1 7 a -hydroxy-4-p regnene-3 ,20-dione
9a-bromo-11/3,21-dif luoro-17a-hydroxy-4-p regnene-3 ,20-dione caproate
9a -b romo-1 Iß , 17a, 21- t r ihydroxy-4-pregnene-3 ,20-d ione
REACTION
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
Δ1; 20 -C=O-* 20ß-OH
1
Δ
1
Δ
1
Δ
Δ1
1
Δ
1
Δ
1
Δ
1
Δ
R E F .
H-377
H-384; H-389; N-665; N-671
B-37; F-231; F-232; H-389; H-399; K-467; N-665; N-670; N-671
N-665; N-670
H-389
R-749
R-749
S-911
R-756
R-756
R-755
R-758
R-756
R-756
N-668
nene-3,20-dione 21-acetate
TABLE I I I
Transformat ions by Genus: CORYNEBACTERIUM
365
SPECIES
simplex
SOURCE
ATCC-6946
SUBSTRATE
9a ,17a -d ib romo- l l /3 ,21 -d i f luo ro -4-pregnene-3 ,20-d ione
9a, l l ß - d i b r o m o - 2 1 - f l u o r o - 6 a -me thy l -4 -p r egnene -3 ,20 -dione
9a -ch lo ro- l l /3 ,21-d i f luoro-17a-hydroxy-4 -p regnene -3 ,20 -dione
9a -ch lo ro - l l | 3 ,21 -d i f luo ro -6a -methyl-4 -pr egnene - 3 , 2 0 -dione
1 Iß-ch lor 0-21 -fluor o - l la -hydroxy-9a- iodo-4-pregnene -3,20-dione
l l /3 -ch loro-21- f luoro-9a- iodo-6 a - m e t h y l - 4 - p r e g n e n e - 3 , 2 0 -dione
9a-ch lo ro- l l /3 ,17α , 21 - tr ihydroxy-4-pregnene-3 ,20-d ione
7a -cyano- l l / 3 ,17a ,21 - t r ihydroxy-4-pregnene-3 ,20-d ione
7ß-cyano - l l ß ,17a ,21 - t r i hyd roxy -4-pregnene-3 ,20-d ione
16-chlor méthylène-11/3 ,17a ,21-t r i h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
9a , l l / 3 -d ich lo ro -6a ,21-d i f luo ro -4-pregnene-3 ,20-d ione
9 a , l l ß - d i c h l o r o - 2 1 - f l u o r o - 1 7 a -hydroxy-4 -p regnene -3 ,20 -dione
9a, l l ß -d i ch lo ro -21 - f luo ro -17a -hydroxy-4-p regnene-3 ,20 -dione ace ta te
9 a , l l ß - d i c h l o r o - 6 a - f l u o r o - 2 1 -iodo-4-pregnene-3 ,20-d ione
9a, l l ß -d i ch lo ro -21 - f l uo ro -6a -me thy l -4 -p r egnene -3 ,20 -dione
9a, l l ß -d i ch lo ro -17a -hyd roxy-21- iodo-4 -p regnene -3 ,20 -dione
REACTION
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
R E F .
R-756
R-755
R-756
R-755
R-756
R-755
N-668
B-75
B-75
W-1084
R-758
R-756
R-756
R-758
R-755
R-756
366
TABLE I I I
Transformat ions by Genus: CORYNEBACTERIUM
SPECIES
simplex
SOURCE
ATCC-6946
SUBSTRATE
9a , l l j3 -d ich loro-21- iodo-6a-methy 1-4-pregnene-3 ,20-dione
9a- f luoro- l l j3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
16- f luormethy lene- l l /3 ,17a ,21-t r ihydroxy-4-p regnene-3 ,20-dione
6a , l l / 3 ,21 - t r i f l uo ro -9a - iodo-4-pregnene-3 ,20-d ione
l l a ,17a ,21 - t r ihydroxy-16 /3 -methyl -4 -pregnene - 3 , 2 0 -dione
l lß ,17a ,21- t r ihydroxy-16 /3 -methoxy-4-p regnene-3 ,20-dione 21-aceta te
11/3,17α, 21 - t r ihy dr oxy -6 -méthyl -ène -4 -pregnene-3 ,20-d ione 21-aceta te
11/3,15/3,17«, 21 - t e t rahydroxy-4-pregnene-3 ,20-d ione
l l j3,16α, 17α, 21 - te t rahydroxy-4-pregnene-3 ,20-d ione
17a-bromo-9a , 11/3-dichloro-21- f luoro-6a-methy l -4-pr e gnene - 3 ,2 0 - dione
9 a - b r o m o - l l j 3 - c h l o r o - 6 a , 2 1 -dif luor o -17a - methyl - 4 -pregnene-3 ,20-d ione
9a-bromo-11/3-chlor o-21-f luoro-17a-hydroxy-6a-methyl -4-pregnene-3 ,20-d ione
9a -b romo- l l /3 -ch lo ro -21- f luoro -17a -hydroxy -6a -methyl -4 -pregnene-3 ,20-d ione aceta te
REACTION
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
y
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
R E F .
R-755
H-389; N-665; N-668; N-669; N-670; N-671
W-1084
R-758
C-109; 1-421
R-760
F-264
C-127
B-54; B-59; B-61
R-759
R-759
R-759
R-759
T r a n s f o r m a t i o n s by Genus:
SPECIES
simplex
SOURCE
ATCC-6946
SUBSTRATE
17a -b romo-9a ,21 -d i ch lo ro -6a , 21-d i f luoro-4-pregnene-3 , 20-dione
9a -b romo- l l /3 ,21-d i f luo ro -17a-hydroxy-6a -me thy l -4 -p reg -nene-3 ,20-d ione
9a -b romo- l l / 3 , 21 -d i f l uo ro -17a -hydroxy-6a -me thy l -4 -p reg -nene-3 ,20-d ione ace ta te
9a -b romo- l l /3 ,21-d i f luoro -17a-hydr oxy - 6a - methyl - 4 -pr e g-nenê-3 ,20-d ione caproa te
9a -b romo-6a , 11/3,21-tr i f luoro-17a-hydroxy-4-p regnene-3 , 20-dione
9 a - b r o m o - 6 a , l l / 3 , 2 1 - t r i f l u o r o -1 l a -hydroxy-4 -p regnene -3 , 20-dione ace ta te
9 a - b r o m o - l l ß , 17a ,21- t r ihydroxy-16a -methyl -4 -pr egnene - 3 , 2 0 -dione
9a, 17a -d ib romo- l l / 3 - ch lo ro -21 -f luoro-6a-methy l -4 -p r egnene-3,20-dione
9a, l l j3-d ibromo-21-f luoro-6a , 17a -dimethy 1-4 -pr egnene -3 ,20-dione
l l /3 -ch loro-6a ,21-d i f luoro-17a-hydroxy-9a- iodo-4-pr egnene-3,20-dione
l l j3 -ch loro-6a ,21-d i f luoro-17a-hydroxy-9a- iodo-4-pr egnene-3,20-dione
9a-ch loro- l l j3 ,21-d i f luoro-6a , 17a-dimethy 1-4-pr egnene-3,20-dione
9a -ch lo ro - l l j 3 - f l uo ro -17a ,21 -d ihydroxy-2a -me thy l -4 -p reg -nene-3 ,20-d ione 21-ace ta te
l l^ -ch loro-21- f luoro-17a-hydroxy-9a - iodo -6a -me thy l -4 -p regnene -3,20-dione
11 ß - chlor o - 21 - fluor o -17a - hydr oxy-9a - iodo-6a -me thy l -4 -p r egnene-3,20-dione aceta te
REACTION
ï 1 Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
REF.
R-759
R-759
R-759
R-759
R-759
R-759
R-752
R-759
R-759
R-759
R-759
R-759
N-691
R-759
R-759
TABLE I I I
CORYNEBACTERIUM
367
368
TABLE I I I
Transformat ions by Genus: CORYNEBACTERIUM
SPECIES
simplex
SOURCE
ATCC-6946
SUBSTRATE
9a-ch lo ro - l l / 3 ,17a ,21 - t r ihydroxy-16a-methyI -4 -p regnene-3 ,20-dione
9a , l l j3 -d ich loro-6a ,21-d i f luoro-17a-hydroxy-4-pregnene-3 , 20-dione
9a , l l /3 -d ich lo ro-6a ,21-d i f luoro-17a-hydroxv-4-pregnene-3 , 20-dione aceta te
9 a , l l ß - d i c h l o r o - 6 a , 2 1 - d i f l u o r o -17α-hydroxy-4-pregnene-3 , 20-dione caproate
9a , l l j3 -d ich loro-6a ,21-d i f luoro-17a-methy l -4 -p regnene-3 , 20-dione
hydroxy-21 -iodo-4 -pregnene -3,20-dione
9a, l l /3-d ichloro-6a-f luoro-17a-hydroxy-21- iodo-4-pregnene -3,20-dione aceta te
9a , l l /3 -d ich loro-21- f luoro-17a-hydroxy-6a -methy l -4 -p reg-nene-3 ,20-d ione
9a, l l /3-dichloro-21-f luoro-17a-hydroxy -6a- methyl-4 -p r eg -nene -3 ,20-dione aceta te
9α, l l /3-dichloro-21-f luoro-17a-hydroxy-6α-methy l -4 -preg-nene-3 ,20-d ione caproate
9a, l l ß - d i c h l o r o - 6 a - f l u o r o - 2 1 -iodo-17a-methy l -4 -pregnene-3,20-dione
9a, l l |3 -d ichloro-21-f luoro-6a , 17a-d imethy l -4 -pregnene-3 , 20-dione
9a, l l j3-dichloro-17a,21-dihydroxy -2a -me thy l -4 -p regnene -3 ,20 -dione 21-aceta te
9α, 11/3-dichlor o - l 7α-hydroxy-21-iodo-6α-methyl -4-pregnene-3,20-dione
9a, 11/3-dichlor o - l 7a -hydroxy -21 -iodo-6a-methyl -4 -pregnene -3,20-dione aceta te
REACTION
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
REF.
R-752
R-759
R-759
R-759
R-759
R-759
R-759
R-759
R-759
R-759
R-759
R-759
N-691
R-759
R-759
9α, l lß-dichloro-6a-fluoro-17a-
TABLE I I I
T r a n s f o r m a t i o n s by G e n u s : CORYNEBACTERIUM
369
SPECIES
simplex
SOURCE
ATCC-6946
SUBSTRATE
9a, l l j3-d ichloro-21- iodo-6a , 17a -dimethyl-4 -pregnene -3 ,20-dione
9 a - f l u o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione
9a- f luoro- l l j3 ,16a , 1 7 a , 2 1 - t e t r a -hydroxy-4 -p regnene-3 , 20-dione
9 a - f l u o r o - l l ß , 1 6 a , 1 7 a , 2 1 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione 16 ,21-diace ta te
6 a - f l u o r o - l l ß , 17a ,21- t r ihydroxy-16a -methyl -4 -pregnene - 3 , 20-dione
9a , l l / 3 -d i f l uo ro -17a ,21 -dihydr oxy - 2a - methyl - 4 -p regnene-3 ,20-d ione 2 1 -aceta te
l l j 3 ,17a ,21- t r ihydroxy-6a -methyl-16 -méthylène -4 -p regnene-3 ,20-d ione
l l / 3 ,17a ,21- t r ihydroxy-16a-methy 1 - 6 - méthylène - 4 -p regnene-3 ,20-d ione
9a-ch loro- l l j3 - f luoro-16a , 17a, 21 - t r ihydroxy -2a -methyl -4 -p regnene-3 ,20-d ione 2 1 -aceta te
9a -ch lo ro - l l / 3 - f luo ro -21 -hydr oxy - 2a - methyl -16a, 17a -i sopropyl idenedioxy-4-preg-nene-3 ,20-d ione ace ta te
6a- f luoro- l l /3 ,14a , H a ^ l - t e t r a -hydr oxy -16a - methyl - 4 -pr e g -nene-3 ,20-d ione
17a, 21 -dihydroxy -16/3 - methyl -5a -9(11) -p regnene-3 ,20-dione 21-aceta te
REACTION
1
Δ
1
Δ
Δ1; 2 0 - C = O -20/3-OH
20-C=O-20 /3 -OH
1
Δ
1
Δ
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
9(11)
Δ - 9 a , 11a-oxidejA1; Δ 4 ; 2 1 - O A c -- 2 1 - O H
9 ( H )
Δ - 9 a . 11a-oxide; Δ ; 21-OAc—21-OH
REF.
R-759
B - 6 1 ; G-296; H-399; S-908
S-908
G-296; S-908
B-57; B-59; B-60
U-1042
N-691
B-69
F-264
N-691
N-691
U-1042
C-138
C-138
370
TABLE I I I
Transformat ions by Genus: CORYNEBACTERIUM
SPECIES
simplex
SOURCE
ATCC -6946
SUBSTRATE
9a - f l uo ro -4 -p regnene -3 ,11 ,20 -t r ione
21 -hydroxy-4 -p regnene -3 ,11 ,20 -t r ione
9a - f luoro-17a-hydroxy-4-preg-n e n e - 3 , 1 1 , 2 0 - t r ione
9a - f luoro-21-hydroxy-4-pregnene - 3 , 1 1 , 2 0 - t r i o n e
17a, 21-dihydroxy-4-pregnene -3 ,11 ,20- t r ione
17a „21 -dihydroxy -4 -pr egnene -3 ,11 ,20 - t r ione 4-C1 4
17a, 21-dihydroxy-4-pregnene -3 ,11 ,20- t r ione 21-aceta te
9a -b romo-17a ,21-d ihydroxy-4 -p r e g n e n e - 3 , l l , 2 0 - t r i o n e
16a -n -butyl -17a, 21 -dihydroxy -4 - p r e g n e n e - 3 , l l , 2 0 - t r i o n e
16a-n - butyl -17a, 21-dihydroxy-4 -pr egnene - 3 , 1 1 , 2 0 - t r ione 21-aceta te
17α, 21 -dihydroxy -16 - méthylène -4-pr egnene-3 ,11 ,20 - t r ione
9a-ch loro-17a , 21 -dihydroxy- 4 -pr egnene - 3 , 1 1 , 2 0 - t r ione
7a-cyano-17a, 21-dihydroxy-4-p regnene -3 ,11 ,20 - t r i one
2a -fluoro -17a, 21 -dihydroxy -4 -p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
9a-fluor o -17a, 21-dihydroxy-4-p r egnene -3 ,11 ,20 - t r ione
7/3-cyano-9a-fluoro-17a, 2 1 -d ihydroxy-4 -p regnene -3 ,11 ,20-t r ione
9a- f luoro- l l /3 ,16a , 17a, 20/3,21-pentahydr oxy -1 ,4 -pr egnadien -3-one
REACTION
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
Δ1; 2 0 - C = O ^ 20/3-OH
Δ1
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
20/3-OH -20-C=O
R E F .
H-379
N-665; N-670
H-379
N-668
H-389; N-665; N-670; N-671
H-389
C-120
N-665; N-670
N-668
N-690; N-692
N-690; N-692
M-558
N-668
B-75
H-401
H-379; N-668; N-669
B-75
G-294; G-296
TABLE I I I
T r a n s f o r m a t i o n s by Genus : CORYNEBACTERIUM
371
SPECIES
simplex
SOURCE
ATCC-6946
SUBSTRATE
9a-f luoro- l l /3 ,16α, 17α,20/3,21-pentahydroxy-1 ,4 -pregnadien-3-one
3ß ,21-d ihydroxy-5 ,16-p regna-dien-20-one diaceta te
9a- f luoro- l l /3 , 16α, 170 ,21 - t e t r a -hydroxy -1 ,4 -pr egnadiene -3,20-dione
9a -b romo- l l / 3 ,17a ,21 - t r i hyd roxy - 4 , 6 - p r egnadiene-3 ,20-dione
6a, 9a-d i f luoro- l l /3 ,17a , 21 - t r i -hydr oxy -4 ,6 -pr egnadiene -3,20-dione
4,9(11)-pr egnadiene-3 ,20-dione
17a-bromo-4 ,9(11)-pregnadiene -3,20-dione
1 7 a - c h l o r o - 4 , 9 ( l l ) - p r e g n a d i e n e -3,20-dione
6ß- f luo ro -4 ,9 ( l l ) - p r egnad i ene -3,20-dione
21-f luoro-4,9(11)-pregnadiene -3,20-dione
17a -hydroxy-4 ,9 ( l l ) -p regnad iene -3 ,20-dione
17a-hydroxy-4,9(11)-pr egnadiene - 3 , 2 0 - dione capr oate
21 -hydroxy-4,9(11) -pregnadiene -3,20-dione
6a-methyl-4 ,9(11) -pregnadiene -3 ,20-dione
6/3-methyI-4,9( l l ) -pregnadiene -3 ,20-dione
17a-methy l -4 ,9 (11)-pregnadiene-3,20-dione
1 7 a - b r o m o - 6 a - f l u o r o - 4 , 9 ( l l ) -p regnad iene-3 ,20-d ione
1 7 a - b r o m o - 6 a - m e t h y l - 4 , 9 ( l l ) -pr egnadiene-3 ,20-dione
REACTION
Δ1 — H
1 5 4
Δ ; Δ ^ Δ ; 3 j3-OAc-3 - C = 0 ; 21-OAc ^ 2 1 - O H
Δ 1 - * H
Δ
Δ
Δ
Δ
Δ1
Δ
Δ
Δ1
Δ
Δ
Δ
Δ
Δ
Δ
Δ
R E F .
G-296
H-388; O-700
G-296
A-7
A-7
R-754; R-773
R-761
R-761
R-757
R-773
R-773
R-761
R-755
R-754; R-755
R-754
R-761
R-759
R-759
372
TABLE I I I
Transformat ions by Genus: CORYNEBACTERIUM
SPECIES
simplex
SOURCE
ATCC-6946
SUBSTRATE
6a - f luo ro -17a -hydroxy-4 ,9 ( l l ) -pregnadiene-3 ,20-d ione
6a - f l uo ro -21 - iodo -4 ,9 ( l l ) -p r egnadiene -3 ,20 -dione
2 1 - f l u o r o - 6 a - m e t h y l - 4 , 9 ( l l ) -pregnadiene-3 ,20-d ione
6a, 21-dif luoro-4,9(11)-pr egna-diene-3 ,20-dione
17a-hydroxy-4,9(11)-pregna-diene-3 ,20-dione cyclo-pentylpropionate
17a -hydroxy-21- iodo-4 ,9 ( l l ) -pr egnadiene -3 ,20-dione
17a -hydroxy-21- iodo-4 ,9 ( l l ) -pregnadiene-3 ,20-d ione aceta te
21 -hydroxy-16a -mercap to -4 ,9 ( l l ) -pr egnadiene-3,20-dione 16,21-diaceta te
2 1 - i o d o - 6 a - m e t h y l - 4 , 9 ( l l ) -pr egnadiene-3,20-dione
6 a , 1 7 a - d i m e t h y l - 4 , 9 ( l l ) -pregnadiene -3 ,20-dione
17a-bromo-6a , 21 -dif luoro-4, 9(11) -pr egnadiene - 3 , 2 0 -dione
17a-bromo-6a-f luoro-21- iodo -4,9(11) -pregnadiene - 3 , 2 0 -dione
17a -bromo-21-f luoro -6a -methyl -4,9(11) -p regnad iene -3 ,20-dione
17a-bromo-21- iodo-6a-methy l -4 , 9 ( l l ) - p r e g n a d i e n e - 3 , 2 0 -dione
9a, l l j3-dichloro-17a-hydroxy-4 ,9(11) -pregnadiene-3 ,20-dione cyclopentylpropionate
6a-f luoro-17a-hydroxy-21- iodo-4,9(11) -p regnad iene -3 ,20-dione
6a-f luoro-17a-hydroxy-21- iodo-4,9(11) -p regnad iene-3 ,20-dione aceta te
REACTION
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
R E F .
H-391
R-758
R-755
R-758
R-761
R-756
R-756
R-764
R-755
R-759
R-759
R-759
R-759
R-759
R-761
R-759
R-759
TABLE I I I
T ransformat ions by Genus: CORYNEBACTERIUM
373
SPECIES
simplex
SOURCE
ATCC - 6946
SUBSTRATE
21 -fluor o -17a -hydroxy - 6a - methyl -4 ,9 (11) -p regnad iene-3 ,20-dione
21 -fluoro - 17a -hydroxy-6a -methyl - 4 , 9 ( l l ) - p r e g n a d i e n e - 3 , 2 0 -dione caproate
6a- f luoro-21- iodo-17a-methyl -4,9(11) -p regnad iene -3 ,20 -dione
21- f luoro-6a ,17a-d imethy l -4 , 9(11) -pregnadiene -3 ,20-dione
6a ,21-d i f luoro-17a-hydroxy-4 , 9 ( l l ) -p regnad iene -3 ,20 -d ione
6a ,21-d i f luoro-17a-hydroxy-4 , 9(11)-pregnadiene-3,20-dione aceta te
6a ,21-d i f luoro-17a-hydroxy-4 , 9(11)-pregnadiene-3 ,20-dione caproate
6a ,21-d i f luo ro -17a-methy l -4 ,9 ( l I -pregnadiene-3 ,20-d ione
17a - hy dr oxy - 21 - iodo - 6a - methy 1 -4 ,9 (11) -p regnad iene-3 ,20-dione
21 - iodo -6a ,17a -d ime thy l -4 ,9 ( l l ) -p regnadiene-3 ,20-d ione
17a,21-dihydroxy-6/3,16a-di-methyl -4 ,9(11) -pregnadiene-3,20-dione 21-ace ta te
17a,21-dihydroxy-6/3,16/3-di-methyl-4,9(11) -pregnadiene -3,20-dione 21-ace ta te
16 - f luo rme thy l - l l / 3 ,17a ,21 - t r i -hydroxy-4 ,15-pregnadiene -3,20-dione
l l ß , 1 7 a , 2 1 - t r i h y d r o x y - 1 6 - m e t h y l -4 ,15-p regnad iene -3 ,20-d ione
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - 6 a , 1 6 - d i -methy l -4 ,15-pregnad iene -3,20-dione
4 ,16-pregnad iene-3 ,20-d ione
17a-hydroxy-9/3,1 l ß - o x i d o - l , 4 , 6 -p regna t r i ene-3 ,20-d ione
REACTION
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
20-C=O — 20j3-OH
R E F .
R-759
R-759
R-759
R-759
R-759
R-759
R-759
R-759
R-756
R-759
N-691
N-691
W-1084
W-1084
B-69
H-388; O-700
G-303
374
TABLE I I I
T r a n s f o r m a t i o n s by Genus : TAXONOMY
CORYNEBACTERIUM CORYNESPORA (Imperfc - Moniliales)
CORYNEUM (Imperf. - Melanconiales)
SPECIES
simplex
species
xe rose
CORYNESPORA
casai icol i
CORYNEUM
cardinale
SOURCE
ATCC-6946
IFO(3530)
soil
NG
CMI(6302)
ATCC-13063t
SUBSTRATE
17a,21-dihydroxy-9j3, 11/3-oxido-1,4,6 -pregnat r iene - 3 , 2 0 -dione
5 -choles ten- 3/3-ol
Diosgenin
3a, 7a, 12a-tr ihydroxy-5/3-cholanic acid
3α, 7α, 12a-tr ihydroxy-5/3-cholanic acid
3 ,7 ,12- t r ike to -5ß-cho lan ic acid
5 -cholesten -3/3-ol
5 - choles ten- 3 j3-ol
Saponins (agave)
17a ,21-d ihydroxy-4-pregnene-3,20-dione
REACTION
2 0 - C = O -2 0/3 -OH
3/3-OH->3-C=0; Δ 5 - Δ 4
3/3-OH->3-C=0; Δ 5 - Δ 4
3/3-OH->3-C=0; Δ 5 - Δ 4 ; Δ1
3a-OH—3-C=p; 7a-OH— H: Δ : Δ4
3a-OH-3-C = 0 ; 7a-OH - Δ6; Δ4
3 a - O H - 3 - C = 0 ; 7 a - O H - H ; Δ4
3a-OH->3-C=0; Δ4
3a-OH—3-C=0
3 a - O H - 3 - C = 0 ; 7 α - Ο Η - Δ 6 ; Δ4
3a-OH—3-C=0; Δ4
7 - C = 0 - 7 a - O H ; Δ4
3/3-OH—3-C=0; Δ5->Δ4
-
3/3-glycoside (saponin) — 3/3-OH
11a-OH
R E F .
G-303
T-1005
N-665; N-670
N-665; N-670
H-358; H-367
H-367
H-367
H-367
H-367
T-974
T-974
T-975
T-975
C-136
T-1030
H-351
T-991
7 - C = 0 ->Δ 6
375
T r a n s f o r m a t i o n s by Genus:
TABLE I I I
CORYNEUM CRINSPORIUM
CUCURBITARIA CUNNINGHAMELLA
TAXONOMY
(Imperf. - Moniliales) (Asco„ - Sphaeriales) (Phyco. - Mucorales)
SPECIES
cardinale
CRINSPORIUM
panorum
CUCURBITARIA
laburni
CUNNINGHAMELLA
africana
albida
bainier i
blakesleeana
SOURCE
ATCC-13063t
NAGAS
C
SSSR
SSSR
ATCC-9244
ATCC-8688a (Up John
H-334)
SUBSTRATE
17a, 21 -d ihydroxy-4-pregnene-3,20-dione 21-ace ta te
4 -p regnene-3 ,20-d ione
not given
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
6a -ch lo ro -17a ,21-d ihydroxy-4 -pregnene-3 ,20-d ione 2 1 -ace ta te
6 a - c h l o r o - 1 7 a , 2 1 - d i h y d r o x y - l , 4 -pregnadiene-3 ,20-d ione
6a-f luoro-16a, 17a, 21 - t r ihydroxy-1,4 -p regnad iene-3 ,20 -dione
6a-f luoro-21-hydroxy-16a, 17a-isopropyl idenedioxy-4-preg-nene-3 ,20-d ione
3a, 11/3,17a-tr ihydroxy-pregnan-20-one
3/3, 11/3,17a-tr ihydroxy-pregnan-20-one
11/3-hydroxy -pr egnane -3 ,20 -dione
11/3,17a-dihydroxy-5a-pregnane-3,20-dione
l l /3 ,21-d ihydroxy-5a-pregnane-3,20-dione
3a, 11/3 ,21- t r ihydroxy-5a-preg-nane-3 ,20-d ione
11/3,17a, 21 - t r ihydroxy-5a-pr eg -nane-3 ,20-d ione
4 -pregnene-3 ,20-d ione
REACTION
l l a - O H - 2 1 - O A c —21-OH
15/3-OH
17a-OH
l l a - O H ; 11/3-OH; l l - C = 0 ( v i a l l / 3 -OH) 6/3-OH; 11/3-OH; l l -C-=0(v ia 11/3-OH) l l /3-OH;21-OAc ^ 2 1 -OH
11/3-OH
11/3-OH
11/3-OH
9α-ΟΗ; 11/3-OH - 1 1 - C = 0
9α-ΟΗ; 11/3-OH - i i -c=o
9α-ΟΗ; 11/3-OH -»ii-c=o
9a-OH; 11/3-OH '■-* n-c=o
9a-OH; 11/3-OH ^n -c=o
9a-OH; 11/3-OH ->n-c=o
9a-OH; 11/3-OH - 1 1 - C = 0
l l / 3 - O H ; l l - C = 0 (via 11/3-OH)
R E F .
T-991
K-486
W-1106; W-1107
E-224
E-224
R-770
R-770
R-771
R-771
H-342
H-342
H-342
H-342
H-342
H-342
H-342
0-696
376
TABLE I I I
Transformat ions by Genus: CUNNINGHAMELLA
SPECIES
blakesleeana
(in mixed cul ture with Baci l lus sphaer icus -ATCC-7055[A1])
SOURCE
ATCC-8688a (Upjohn-H-334)
SUBSTRATE
1 l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
21-hydroxy-4-p regnene-3 ,20-dione
11/3,17a -dihydr oxy -4 -pregnene -3,20-dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
(effect of nutr ients - Ref. 0 -696 and S-919)
(use of vitamin K to inhibit by -products - Ref. S-920)
(effect of ethanol and phenols -Ref. M-556)
(effect of enzyme inhibi tors -Ref. M-555)
(effect of ethanol and phenols -Ref. M-556)
(effect of environment and nutr ients)
19,21-dihydr oxy-4-pregnene-3,20-dione
11/3,17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
11a,21-dihydroxy-4,17(20)-pregnadien-3-one
11/3,21-dihydroxy-4,17(20)-pregnadien-3-one
11α, 22 -dihydroxy -bisnor -4 -cholen-3-one
REACTION
9 a - O H ; l l a - O H -n-c=o 11/3-OH
14a-OH
ll/3-OH(0218)
9a-OH; 11/3-OH -n-c=o 6/3-OH
11/3-OH
11/3-OH; 11 - C = 0 (via 11/3-OH)
1 1 - C = 0 (via 11/3-OH); 6/3-OH; 14a-OH
—
11/3-OH
9a-OH
l lß -OH—11-C=0
9a-OH; 11/3-OH
^n-c=o 9a-OH
9a-OH; 11/3-OH -n-c=o 6/3-OH
R E F .
H-342
M-555
M-555
H-3 74
H-342
H-339; S-919
M-556; N-659; 0 -696 ; S-919; S-920
H-339; M-555; M-556; S-919
S-919
K-466
B-40
H-344
H-344
H-342
H-342
H-342; H-344
M-578
TABLE I I I
Transformat ions by Genus: CUNNINGHAMELLA
377
SPECIES
blakesleeana
(ATCC number 1 repor ted a s elegans 1 in catalog)
SOURCE
ATCC-8688b
ATCC-9245
SUBSTRATE
6a, 16a -d ime thy l -4 -p regnene-3 , 20-dione
16a, 17a-methy lene-4-pregnene-3,20-dione
6a-ch loro-16a , 17a-methylene-4-pregnene-3 ,20-d ione
6a-f luoro-16a, 17a-méthylène-4-pregnene-3 ,20-d ione
6ß-f luoro-16a, 17a-méthylène -4 -p regnene-3 ,20-d ione
6a-methyl -16a , 17a-méthylène -4 -pregnene-3 ,20-d ione
16a, 17a -mé thy lène -1 ,4 -p re gna-d iene-3 ,20-d ione
6a-f luoro-16a, 17a-méthylène -1 ,4-pregnadiene-3 ,20-d ione
6/3-fluoro-16a, 17a-méthylène-1,4 -pregnadiene -3 ,20-d ione
6a-methyl -16a , 17a-methylene-1 ,4-pregnadiene-3 ,20-d ione
16α, 17α-mé thy lène -4 ,6 -p regna-d iene-3 ,20-d ione
6-chloro-16a , 17a-méthylène-4 ,6 -pregnadiene -3 ,20-dione
6-f luoro-16a, 17a -mé thy lène -4 ,6 -pregnadiene-3 ,20-d ione
6-methyl-16a, 17a-méthylène-4 , 6 -pregnadiene -3 ,20-dione
1 6 a , 1 7 a - m e t h y l e n e - l , 4 , 6 - p r e g n a -t r i ene -3 ,20-d ione
6-f luoro-16a, 17a -me thy lene - l , 4 , 6 -p regna t r i ene -3 ,20 -d ione
6-methyl-16a, 17a -me thy lene - l , 4 , 6 -p r egna t r i ene -3 ,20 -d ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21 -dihydroxy - 7 - methyl -4 -pregnene-3 ,20-d ione 21-ace ta te
REACTION
11/3-OH
llj3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
R E F .
S-923
C-92
C-92
C-92
C-92
C-92
C-92
C-92
C-92
C-92
C-92
C-92
C-92
C-92
C-92
C-92
C-92
M-641; M-645
B-33
378
TABLE I I I
T ransformat ions by Genus: CUNNINGHAMELLA
SPECIES
b lakes leeana (ATCC number repor ted as elegans in catalog)
(in sequential fermentation with Ophiobolus he rpo t r i -chus [21-OH] and Tr icothecium roseum [17a-OH])
(in sequential fermentation with
[17α -OH])
(in sequential fermentation with Tr icothecium r o s e u m [17Ö-OH] and Calonectr ia decora [A1])
(in sequential fermentation with Tr icothecium r o s e u m [17a-OH] )
(in sequential fermentation with Ophiobolus he r po t r i -c h u s [ 2 1 - O H ] a n d Tr icothecium r o s e u m [17a-OH])
* *
*
*
1 *
SOURCE
ATCC-9245
C
CBS
SUBSTRATE
17a ,21-d ihydroxy-4 ,14-pregna-d iene-3 ,20-d ione
17a ,21 -d ihyd roxy-4 ,9 ( l l ) -p r egna -d iene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
21-hydroxy-4 -p regnene-3 ,20-dione
21-hydroxy-4-p regnene-3 ,20-dione
d, 1-21-hydroxy-4-pregnene-3,20-dione
18 ,21-d ihydroxy-4-pregnene-3,20-dione
21-hydroxy-3 ,20-d ike to -4 -p reg-nen-18-a l
21 -hydroxy -3 ,20-d ike to-4 -p reg -nene-18-a l aceta te
1,4 -pr egnadiene -3 ,20-dione
4-pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
REACTION
14
Δ —>14a,15a-oxide
11/3-OH; Δ " - » 14a,15a-oxide
9 (11)
Δ 7—9/3,11/3-oxide
11/3-OH; 11/3-OH
-n-c=o
11/3-OH; 11/3-OH - 1 1 - C = 0
11/3-OH; 11/3-OH
^n-c=o
d , l - d - l l / 3 - O H ; l l - C = 0 ( v i a 11/3-OH) + 1
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11a-OH
11/3-OH
l l / 3 - O H ; l l - C = 0 (via 11/3-OH)
6/3-OH
11/3-OH
R E F .
ß - 6 6 ; S-865
S-865
ß - 6 6
W-1106
W-1106
W-1107
W-1102
W-1100
W-1100
W-1100
W-1106
C-98
C-98
C-98
C-98
C-98 1
Tricothecium roseum
TABLE I I I
T r a n s f o r m a t i o n s by Genus : CUNNINGHAMELLA
379
SPECIES
blakesleeana
(Lendner)
(in sequential fermentation with Tr ichoderma glaucum [17a-OH] and Wojnowicia graminis - NRRL-2472 [21-OH])
1 *
1 *
1 *
1 *
1 * 1 * 1 * 1 *
1 * 1 *
SOURCE
CZAS
IFO
MCC
NG
OIAB(l)
OIAB(2)
PEU
QM-631
SUBSTRATE
4-pregnene-3 ,20-d ione
3j3,14/3-dihydroxy-5/3-20(22)-cardenolide
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
(mechanism of hydroxylation)
4 -p regnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3 ,20-dione
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide
4-pregnene -3 ,20-dione
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide
4 -p regnene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
4 -p regnene-3 ,20-d ione (method to obtain higher y i e ld s -dilution cul ture)
REACTION
11/3-OH
16/3-OH
11/3-OH
14a -OH
11/3-OH
11a-OH; 14a-OH; 6 ß , l l a - d i O H
l l a - O H
7/3-OH
lß,7/3-diOH; 5/3,7/3-diOH
3/3-OH^3-C=0
l l a - O H ; 14a-OH; 6/3,11a-diOH
6/3-OH
7/3-OH
1/3,7/3-diOH; 50,7/3-diOH
3 /3 -OH-3-C=0
l l a - O H
11/3-OH
l l / 3 - O H ; l l - C = 0 (via 11/3-OH)
6/3-OH
11/3-OH
11-OH
R E F .
T-1028
N-651
M-566
N-661
B-64
N-682
N-682
N-682
N-682
N-682
N-682
N-682
N-682
N-682
N-682
C-98
C-98
C-98
C-98
C-98
W-1066
380
TABLE I I I
Transformat ions by Genus: CUNNINGHAMELLA
SPECIES
blakesleeana
echinulata
*
*
*
*
*
(Thaxter - 7)
(In mixed cul ture with Bacil lus sphaer icus - ATCC-7055 [ Δ1])
1 1
SOURCE
SSSR
UC
VEB
SSSR
ATCC-1387
FRI
IPB
NG
NRRL
SUBSTRATE
1 7a, 21 -dihydroxy -4 -pregnene -3,20-dione
4-pregnene-3 ,20-d ione
l l cz -hydroxy-4-pregnene-3 ,20-dione
6/3-methyI-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
4-pregnene-3 ,20-d ione
3,20-dione
4-pregnene-3 ,20-d ione
1 l a -hydroxy-4 -p regnene -3 ,20 -dione
21-hydroxy-4-p regnene-3 ,20-dione
17a, 21-dihydroxy-4-pre gnene-3,20-dione
17a, 21 - d ihydroxy-4-pregnene-3,20-dione
4-pregnene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
Sarsasapogenin
Diosgenin
4-dehy dr otigogenone
REACTION
l l / 3 -OH; l l -C = 0 (via 11/3-OH
11/3-OH
6/3-OH
l l ß - O H
11/3-OH
l l / 3 - O H ; l l - C = 0 (via 11/3-OH)
6/3,14a-diOH
l i a - O H
l i a - O H
l l a - O H
l l a - O H
l l a - O H
6/3-OH; l l a - O H
l l a - O H
11/3-OH
l l / 3 - O H ; l l - C = 0 (via l lß -OH)
6/3-OH
11/3-OH
l l a - O H
-
-
—
R E F .
E-224
E-202
E-202
L-520
M-601
M-601; M-636; M-641
S-811
E-224
Z-1125
Z-1125
Z-1125
Z-1125
S-849
C-98
C-98
C-98
C-98
C-98
K-466
M-587
M-587
M-587
echinata 17a,21-dihydroxy-4-pregnene-
TABLE I I I
T r a n s f o r m a t i o n s by Genus : CUNNINGHAMELLA
381
SPECIES
elegans (Lendner)
* * *
* *
1 *
homothallica
r a m o s a
SOURCE
C
CZAS
OIAB
SSSR
VEB
SSSR
CZAS
SUBSTRATE
15a-hydroxy-4-andros tene-3,17-dione
6a-f luoro-14a, 17α, 21-tr ihydroxy -16a- methyl -4 -p regnene-3,20-dione
4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -p regnene-3,20-dione
4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
14/3-hydroxy -3 -keto-5/3-20(22) -cardenolide
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
l i a , 17a ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
11/3,17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
l l / 3 , 17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione 21-aceta te
11/3,17α, 21 - t r i hyd roxy -1 ,4 -pr e gnadiene - 3,2 0 - dione
4 -pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
REACTION
11/3-OH
l l a - O H
11/3-OH
l l a - O H
11/3-OH
l l / 3 - O H ; l l - C = 0 (via 11/3-OH)
6/3-OH
11/3-OH
l l a - O H ; 14a-OH; 6/3, l la-diOH
6/3-OH; l l a - O H
7/3-OH
7/3-OH
l l a - O H ; 11/3-OH; 11-C^O (via l l ß -OH)
-
1 1 - C = 0 (via 11/3-OH)
2 1 - O A c -21-OH
11/3-OH-> l l - C = 0 ; 2 1 - O A c -»21 -OH
-
6ß,14a-diOH
6/3-OH; 11/3-OH; 1 1 - C = 0 (via 11/3-OH)
6/3-OH; l l a - O H ; 11/3-OH; 1 1 - C = 0 (via 11/3-OH)
R E F .
U-1043
U-1042
U-1042
C-98
C-98
C-98
C-98
C-98
N-682
N-682
N-682
N-682
E-224; E-225
E-225
E-225
E-225
E-225
E-225
S-811
E-224
C-98
382
TABLE I I I
T r a n s f o r m a t i o n s by Genus : CUNNINGHAMELLA CURVULARIA
TAXONOMY
(Imperf0 - Moniliales)
SPECIES
r a m o s a
species
ver t ic i l la ta
CURVULARIA
brachyspora (in sequential fermentat ion with Ophiobolus he rpo t r i -chus[21-OH])
(in mixed cul ture with Mycobacterium)
falcata *
(in sequential fermentation with Mycobacterium sp.
f al lax *
geniculata
SOURCE
SSSR
NRRL
P a r k e - Davis (M-2047)
SSSR
C
P F
C
QM-102H
VEB
C
VEB
IFO(6284)
SUBSTRATE
17a, 21-dihydroxy-4-pregnene -3,20-dione
plant saponins
16α, 17α, 21 - [ 3 , 1 , 1 -2 -pyrazolino] 4 -p regnene-3 ,2 0-dione
17a,21 -dihydroxy -4-pregnene -3,20-dione
4-pregnene-3 ,20-d ione
18-0X0-4-pregnene 3 ,20-dione
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
17a ,21 -d ihyd roxy -4 ,9 ( l l ) -pregnadiene-3 ,20-d ione
21-hydroxy-4-pregnene-3 ,20 -dione
21-hydroxy-4 -p regnene-3 ,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20 dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
4-pregnene-3 ,20-d ione
21-hydroxy-4-pregnene-3 ,20-dione
4-pregnene-3 ,20-d ione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
REACTION
6ß-OH; l l ß - O H ; l l - C = 0 ( v i a l lß -OH)
-l l ß - O H
l l a - O H ; l l ß - O H
l l ß - O H
l l ß - O H
l l ß - O H
9(H) Δ '-.9/3,11/3-oxide
7a-OH
l l ß - O H
l l ß - O H
l l ß - O H
l l ß - O H ; 14a-OH; 7 a , l l ß - d i O H ; 7a,14a-diOH; l l ß , 14a -d iOH; 6ß,14a-diOH
7a-OH
l l ß - O H ; 14a-OH; 7a, 14a-d i O H ; l l ß , 1 4 a -diOH
6ß-OH; l l ß - O H ; 14a-OH
R E F .
E-224
K-478
M-593
E-224
W-1106; W-1107
W-1107
S-868
S-865
M-585
S-878
S-878
S-868
Z-1132
M-585
Z-1132
K-469
1
Δ
TABLE I I I
T ransformat ions by Genus: CURVULARIA
383
SPECIES
geniculata
inaequalis
lunata
(in mixed cul ture with one or more of the following: Al te rnar ia pass i f lorae [Δ 1 1 λ
Calonectr ia decora[A Didymella lycopers ic i [ Δ 1 ] , Leptosphaer ia maculans [ l7a-OH ] , Ophiobolus he rpo t r i -c h u s [ 2 1 - O H ] , Tr icothecium r o s e u m [ l7o-OH|)
*
(in mixed cul ture with Leptosphaer ia maculans [17«-OH ] )
SOURCE
VEB (C)
VEB(XCI)
VEB-(XCXXXIII)
V E ß -(XCIV)
ATCC
ATCC-12017
C
SUBSTRATE
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
6/3-hydroxy-3a,5a-cyclopregnan-20-one
17a, 21 -dihydroxy -6a , 16a -d i -methyl - 4 - p r e g n e n e - 3 , 2 0 -dione 21-aceta te
4 -p regnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
d, 1-21-hydroxy-4-pregnene-3,20-dione
6/3,21-dihydroxy-4-pregnene -3 ,20-dione
d, 1-17a, 21 -dihydroxy -4 -pregnene -3,20-dione
REACTION
11/3-OH; 14a-OH; 7a,14a-diOH; 6/3,14a-diOH; l l ß , 1 4 a - d i O H
11/3-OH; l l /3 ,14a-diOH
14a-OH; 6/3,14a-diOH; 7a,14a-diOH
11/3-OH; l l /3,14a-diOH
11/3-OH
11/3-OH
l l / 3 - O H ; l l - C = 0 (via 11/3-OH)
l l a - O H : metaboli te - X
l l ß - O H
l l ß - O H ; 21-OAc - 21-OH
l l ß - O H
7α-ΟΗ
11/3-OH
d , l - d - l l ß - O H + 1
l l ß - O H
d , l — d-l l /3-OH + 1
R E F .
Z-1132
Z-1132
Z-1132
Z-1132
C-98
C-98
C-98
C-98
W-1070
S-805
W-1106; W-1107
M-585
W-1106
W-1106
N-654
W-1102
384
TABLE I I I
Transformat ions by Genus: CURVULARIA
SPECIES
lunata
*
*
*
*
(in sequential ferment-ation with Actinoplanes missour i ens i s -Α Τ Ο Ο - Ι δ β δ ΐ Δ 1 ] )
SOURCE
C
EM
IFO (6286)
KAG(49)
LRL
MCC
NRRL-2380
SUBSTRATE
19 ,21-d ihydroxy-4-pregnene-3,20-dione
6a- f luoro-17a ,21-dihydroxy-16a-methyl -4 -pr egnene - 3,20 -dione
2 1 - h y d r o x y - l , 4 - p r e g n a d i e n e -3,20-dione
1 la -hydroxy -16 -méthylène -4 -p regnene-3 ,20-d ione
1 la, 21 -dihydr oxy -16 - méthylène -4-pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
14a ,17a ,21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
6a- f luoro-17a ,21-d ihydroxy-16a-me thy l -4 -p regnene -3 ,20 -dione
17a, 21-dihydroxy-4-pregnene -3,20-dione (effect of nutr ients - t r a ce elements)
17/3-hydroxy-4-estren-3-one
REACTION
11/3-OH
11/3-OH
14α-OH
11/3-OH
11/3-OH
11/3-OH
9α-ΟΗ
Πα-ΟΗ
11/3-OH
14α-ΟΗ
6/3-OH
11α-ΟΗ; 14α-ΟΗ
6/3,14a-diOH
7a,14a-diOH
7α-OH
6/3-OH
11/3-OH
11/3-OH
l l ß - O H
10/3-OH
l l ß - O H
14α-ΟΗ
10/3,11/3-diOH
R E F .
N-654
U-1042
U-1042
W-1106
B-68
M-558
K-469
K-469
K-469
K-469
K-469
K-469
K-469
K-469
K-469
K-469
M-536
M-536
D-192
D-150
D-150
D-150
D-150
TABLE I I I
T ransformat ions by Genus: CURVULARIA
385
SPECIES SOURCE SUBSTRATE REACTION R E F .
lunata NRRL-2380 17a-ethyl-17/3-hydroxy-1,4-andros tad ien-3-one
17a -hyd roxy - l -5a -p regnene -3,20-dione ace ta te
1 7 a - m e t h y l - l - 5 a - p r e g n e n e - 3 , 20-dione
21 - f luo ro -19-nor -4 -p regnene -3,20-dione
17a-hydr oxy -19 -nor_-4 -pr egnene -3,20-dione
4 -pregnene-3 ,20-d ione
17a-bromo-4-pregnene - 3 , 2 0 -dione
1 la -chloro -4-pregnene - 3 , 2 0 -dione
17a -hydroxy-4 -p regnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
6 /3-methyl -4-pregnene-3 ,20-dione
17a -b romo-6a - f l uo ro -4 -p reg -nene-3 ,20-d ione
1 la -bromo -6a -methyl -4 -pr eg -nene-3 ,20-d ione
6a - f luo ro -17a -me thy l -4 -p reg -nene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3,20-dione (compare reac t ion with C. lunata - IFO-6286-Ref. K-469)
(effect of ant ibiot ics - Ref. B-37o In mixed cul ture with Baci l lus sphaer icus - ATCC-7055 - Ref. K-444)
11/3-OH
11/3-OH
11/3-OH
N-677a
11/3-OH
11/3-OH
11]3-ΟΗ
11/3-OH
14α-ΟΗ
7a,14a-diOH
11/3-OH
11/3,14a-
11/3-OH
diOH
R-761 ; R-773
R-761
R-755
R-761 ; R-773
D-187
D-187
S-871
D-187
R-756; R-773
R-761
11/3-OH
l l /3,14a-diOH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
l l a - O H
S-871
S-876
S-871; S-875
R-754; R-757; R-773
R-759
R-756; R-759
R-759
K-443; K-469
B-37; K-443; K-444
386
TABLE I I I
Transformat ions by Genus: CURVULARIA
SPECIES
lunata
SOURCE
NRRL-2380
SUBSTRATE
17a, 21 -dihydr oxy -4 -pr egnene -3,20-dione (compare reac t ion with C0 lunata - IFO-6286-Ref. K-469)
(in mixed cul ture with M. phlei - Ref. S-868)
(with cel l free enzyme)
(compare reac t ion with IFO-6286 - Ref. K-469)
(compare react ion with IFO-6286 - Ref0 K-469)
(effect of t r a c e e lements -solvents)
(compare react ion with IFO-6286 - Ref. K-469)
(effect of t r a c e e lements -so lven ts ; compare react ion with IFO-6286 - Ref0 -K-469)
(enzyme prepara t ion)
17a-hydroxy-21-methyl -4-pregnene-3 ,20-d ione
21-hydroxy-17a-methy l -4 -p reg-nene-3 ,20-d ione aceta te
1 la -hydroxy -16 -méthylène -4 -pregnene-3 ,20-d ione
6a, 17a-dimethyl -4-pregnene -3,20-dione
6/3-fluoro-17a-hydroxy-21-methyl-4-pregnene-3 ,20-d ione
21-hydroxy-16a ,17a-oxido-4-pregnene-3 ,20-d ione aceta te
REACTION
11/3-OH
11/3-OH
11/3-OH
14a-OH
6j3,14a-diOH
7a, l l j3-diOH
7a,14a-diOH
11/3,14a-diOH
20-C=O — 20/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH; 21-OAc — 21-OH
14a-OH;21-OAc — 21-OH
ll j6-OH;14a-OH; 21-OAc^21-OH
l l /3,14a-diOH; 21-OAc-»21-OH
R E F .
K-466; K-469
S-868; S-871; S-875; S-879
Z-1134
K-443; K-469; Z-1134
K-469
K-443
K-469; S-879
Δζ2; K-443; K-469; S-879; S-877
T-1017; Z-1134
H-391
H-377
B-68
R-759
H-391
A-3
A-3
A-4; A-5
A-3
TABLE I I I
Transformat ions by Genus: CURVULARIA
387
SPECIES
lunata
SOURCE
NRRL-2380
SUBSTRATE
17a ,21-d ihydroxy-16a-methyl -4 -pregnene-3 ,20-d ione
17a ,21-dihydroxy-16-methyIene-4-pregnene-3 ,20-d ione
15/3,17a, 21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
1 6 a , 1 7 a , 2 1 - [ 3 , l , l - 2 - p y r a z o l i n o ] 4 -p regnene-3 ,20-d ione
16-chlor méthylène-17 a , 21 -d i -hydroxy-4 - p r e g n e n e - 3 , 2 0 -dione
6a - f luoro-17a ,21-d ihydroxy-21-methyl-4 -pregnene - 3 , 2 0 -dione 21-ace ta te
6a- f luoro-17a ,21-d ihydroxy-16-methylene -4 - p r e g n e n e - 3 , 2 0 -dione
16 -fluor o méthylène-17 a, 21 -d i -hydroxy-4 - p r e g n e n e - 3 , 2 0 -dione
17a, 21-dihy dr oxy - 6a - methyl -16 -méthylène -4 -pregnene - 3 , 2 0 -dione 21-aceta te
17α-hydroxy-16-mé thy lène-1 ,4-pregnadiene-3 ,20-d ione
17a, 21-d ihydroxy-4 ,9(11)-pregna-d iene-3 ,20-d ione
17a, 21-d ihydroxy-4 ,9(11) -pregna-d iene-3 ,20-d ione [11,12a-H3] 21-ace ta te
4 ,11 -pregnadiene -3 ,20-dione
REACTION
l l ß - O H
15a-OH
ll /3,14a-diOH
l l ß - O H
l l ß - O H
l l ß - O H
l l ß - O H
l l ß - O H ; 21-OAc - 21-OH
11/3-OH
11/3-OH
l l ß - O H ; 21-OAc — 21-OH
l l ß - O H
9(11) Δ - 9/3,11/3-oxide
14a-OH 9(11)
14a-OH; Δ — 9ß ,1Iß-ox ide
9(11)
Δ —9/3, U ß " oxide; 21-OAc —21 -OH
21-OAc—21-OH
Δ *—11/3,12/3-oxide
R E F .
C-96
C-96
C-96
T-981
C-126
W-1113
W-1084
H-390
A-7
W-1084
B-69
B-68
B-65; B-66; S-865
B-65
B-65
K-484
K-484
K-484
388
TABLE I I I
Transformat ions by Genus: CURVULARIA
SPECIES
lunata
SOURCE
NRRL-2380
NRRL-2434
OR
SAG
SY(192)
SY(961-29E)
Takeda
UC
SUBSTRATE
17a, 21-d ihydroxy-4 ,14-pregna-diene-3 ,20-dione
17a, 21-dihydroxy-16-methyl-4 ,15-pregnadiene-3 ,20-d ione
16-fluor methyl-17a, 21-dihydroxy-4 ,15-pregnadiene-3 ,20-d ione 21-aceta te
17α, 21-dihydroxy-6α, 16-dimethyl -4 ,15 -p regnad iene -3 ,20 -dione
17a ,21-d ihydroxy-4 ,6 -pregna-diene - 3 , 1 1 , 2 0 - t r ione
1 ,4 ,16 -p regna t r i ene -3 ,20 -dione
9 a - b r o m o - l l ß , 1 7 a , 2 1 - t r i h y d r o x y -1 , 4 , 6 - p r e g n a t r i e n e - 3 , 2 0 -dione
9a -ch lo ro -17a ,21 -d ihydroxy- l , 4 , 6 - p r e g n a t r i e n e - 3 , 1 1 , 2 0 -t r ione
9a -f luoro- 17a, 21 -d ihydroxy-1 , 4 , 6 -pregnat r iene - 3 , 1 1 , 2 0 -t r ione
17a, 21 -dihydroxy -6a, 16a -di -me thy l -4 -p regnene -3 ,20 -dione
17a, 21 -dihydroxy-16a-methyl -l , 4 -p regnad iene -3 ,20 -d ione 21-aceta te
17ß-hydroxy-17a-methyl -4-andros tene-3-one
17α, 21-d ihydroxy- la -methy l -4 -pregnene-3 ,20-d ione
19-nor -4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
17a, 21-dihydroxy-7-methyl-4 -pregnene-3 ,20-d ione 2 1 -aceta te
REACTION
14
Δ —» 14a, 15a-oxide
11/3-OH; Δ 1 4 -14a,15a-oxide
l l ß - O H
ll /3-OH;21-OAc -> 21-OH
11/3-OH
2 0 - C = O -20/3-OH
l l ß - O H
14a-OH
14a-OH
14a-OH
l l ß - O H
11/3-OH
16ß-OH
16ß-OH; 16ß-OH -^16 -C=0
l l ß - O H
l l ß - O H
11/3,21-diOH
14a-OH
l l ß - O H ; 21-OAc - 21-OH
R E F .
B-66; S-865
S-865
W-1084
W-1084
ß-69
G-306
H-388; O-700
G-301; G-302
G-301; G-302
G-301; G-302
S-903
S-904
S-950
S-950
W-1112
B - 7 1 ; B-73
R-783
N-661
B-33
TABLE I I I
Transformat ions by Genus: CURVULARIA
389
SPECIES
lunata
*
*
*
*
*
maculans
oryzae
pa l lescens *
SOURCE
VEB
VEB (XCIII)
VEB(XCV)
VEß (CII)
VEB CIII
IFO (6292)
VEB(CXXXI)
C
SUBSTRATE
4-pregnene-3 ,20-d ione (effect of inhibi tors and Fe -Ref. Z-1130)
17α, 21 -dihydroxy -4 -pregnene -3,20-dione 21-aceta te
4 -pregnene-3 ,20-d ione (comparison of different spec ies and s t ra ins-ef fec t of nu t r i en t s - t r ace e lements -p H-inhibitor s - cofactor s -subs t ra te specificity-Ref. Z-1132)
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
(plus other s u b s t r a t e s -products of which a r e un-known or questionable s t ruc tu re -See page 262 of Ref. Z-1132)
17a, 21-dihydroxy-4-pregnene -3,20-dione (comparison of different s t r a ins - Ref. K-469)
4 -pregnene-3 ,20-d ione
21-hydroxy-4-p regnene-3 ,20-dione
12a-f luoro- l l /3-hydroxy-4-pregnene-3 ,20-d ione
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
11/3,21 -dihydroxy -3 ,20-dike to -4 -pregnen-18-a l
REACTION
11/3-OH
6j3,14a-diOH
7a,14a-diOH
ll /3,14a-diOH
11/3-OH; 21-OAc - 21-OH
11/3-OH; 14a-OH
7a,14a-diOH
6/3,14a-diOH
l l ß , 14a -d iOH
7a,14a-diOH
ll /3,14a-diOH
7a,14a-diOH
ll /3,14a-diOH
7a,14a-diOH
ll /3,14a-diOH
6j3-OH;l la-OH; 14a-OH; 6/3, 14a-diOH; 7a, 14a-diOH
11/3-OH; 11)3, 14a-diOH
7a-OH
14a-OH
14a-OH
14a-OH
R E F .
Z-1130
S-811
Z-1130
Z-1130
Z-1131
Z-1132
Z-1132
Z-1132
Z-1132
Z-1132
Z-1132
Z-1132
Z-1132
Z-1132
Z-1132
K-469
Z-1132
M-585
W-1103
W-1108a
W-1108
390
TABLE I I I
T r a n s f o r m a t i o n s by G e n u s : CURVULARIA
SPECIES
pal lescens
(in mixed cul ture with Mycobacterium sp. -
M) *
*
*
*
species
*
*
t e t r a m e r a
* *
*
*
t r ifoli i *
*
*
uncinata *
* *
*
SOURCE
NRRL-2381 (QM-371-D)
P F
VES(XCVI)
CI
P F
VEB
FRI
VEB (CO)
IFO(6241)
VEB( CXXXIV)
SUBSTRATE
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
17a ,21 -d ihydroxy-4 ,9 ( l l ) -pregnadiene -3 ,20-dione [11,12a-H3] 21-aceta te
4-pregnene-3 ,20-d ione
14a-hydroxy-4-pregnene-3 ,20-dione
17a, 21-dihydroxy-4-pregnene-3,20-dione
4-pregnene-3 ,20-d ione
17a, 21-dihydr oxy-4-pregnene-3,20-dione (compare with other spec i e s -Ref. K-469)
4-pregnene-3 ,20-d ione
REACTION
11/3-OH
11/3-OH
11/3-OH
14a-OH
6ß,14a-diOH
7a,14a-diOH
ll /3,14a-diOH
14a-OH
7a,14a-diOH 9 ( l l )
Δ - 9 ß , l l / 3 -oxide; 21-OAc -» 21-OH
7a,14a-diOH
7a-OH
-
11/3-OH
14a-OH
6ß,14a-diOH
7a,14a-diOH
11/3,14a-diOH
6/3-OH
11a-OH
14a-OH
6/3,14a-diOH
7a,14a-diOH
11/3-OH
14a-OH
6/3,14a-diOH 7a,14a-diOH ll /3,14a-diOH
R E F .
S-875
S-868
Z-1132
Z-1132
Z-1132
Z-1132
Z-1132
Z-1132
Z-1132
K-484
S-813
S-813
S-849
Z-1132
Z-1132
Z-1132
Z-1132
Z-1132
K-469
K-469
K-469
K-469
K-469
Z-1132
Z-1132 Z-1132 Z-1132 Z-1132
391
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus : CYLINDROCARPON (imperf» - Monmaies)
SPECIES SOURCE SUBSTRATE REACTION R E F .
radic icola ATCC-11011 17/3-hydroxy-4-androsten-3-one
(with cel l free enzyme)
4 -andros tene-3 ,17-d ione (with KCN to inhibit Δ Ref. S-898)
D-homo-17a -oxa -4 -andros t ene -3,17-dione
1,4 -androstadiene -3 ,17 -dione
17ß-hydroxy- l , 4 -andros t ad ien -3-one
5a-pregnane-3 ,20-d ione (with cel l free enzymes)
5j3-pregnane-3,20-dione (with cell free enzymes)
19 -nor -4 -p regnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione (with cell free enzymes -see Ref0 S-890)
4 -pregnene-3 ,20-d ione 20-cycloethyleneketal
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
Δ ; 17/3-OH -» 17a -oxa -17 -C=0
9a-OH
Δ ; 1 7 - C = 0 -17a -oxa -17 -C=0
F-269; F-274; F-284
S-890
P-740 ; S-898
H-398
H-398
1 7 - C = 0 - > 17a-o x a - 1 7 - C = 0
17/3-OH -> 1 7 - C = 0
17/3-OH-* 17a-o x a - 1 7 - C = 0
J j 4
Δ
4 1 4
Δ ; Δ '
9a-OH
1
Δ
Δ1; 17i3-Ac— 17a -oxa -17 -C=0
Δ ; 17/3-Ac -» 17/3-OH
Δ ; 17/3-Ac -> 1 7 - C = 0
1
Δ
1
Δ
1
Δ ; 17a-OH-17j3-(20-C=O-21-OH) -*17a-oxa-17-c=o
P-733
P-733
P-733
S-890
S-890
P-740; S-898
P - 7 3 3 ; S-890
F - 2 5 1 ; F-269; F-274; F-284; H-398; P-733
P-733
P-733
F-251
F-275
F-269; F-275; F-284
1
Δ
1
Δ
392
TABLE I I I
T r a n s f o r m a t i o n s by Genus: TAXONOMY
CYLINDROCARPON A
CYLINDROCEPHALUM (Imperf0 - Moniliales)
SPECIES
radicicola
CYLINDROCEPHALUM
aureum
SOURCE
ATCC-11011
ATCC-12720 (QM-610)
SUBSTRATE
17a, 21 -dihydroxy-4-pregnene -3,20-dione 21-aceta te
16α, 17a-ox ido-4-pregnene-3 ,20-dione
9a -b romo- l l / 3 -hydroxy-4 -p reg -nene-3 ,20-dione
9a -ch lo ro - l l /3 -hydroxy-4-p reg-nene-3 ,20-dione
9 a - f l u o r o - l l ß - h y d r o x y - 4 - p r e g -nene-3 ,20-dione
9a- f luoro- l l /3 ,16a-d ihydroxy-4-pregnene-3 ,20-d ione (use of cel l free enzyme)
6a ,9a -d i f luoro- l l /3 ,16a-d i -hydroxy-4-p regnene-3 ,20-dione (with cell free enzymes)
4 -p regnene -3 ,11 ,20 - t r ione
9 a - b r o m o - 4 - p r e g n e n e - 3 , 1 1 , 2 0 -t r ione
9o -ch lo ro -4 -p regnene -3 ,11 ,20 -t r ione
9a - f luo ro -4 -p regnene -3 ,11 ,20 -t r ione
5-choles ten-3ß-ol
4-pregnene-3 ,20-d ione
21-hydroxy-4-pregnene-3 ,20-dione
REACTION
Δ1; 21-OAc — 21-OH
16a,17a-oxido-17/3-Ac -16a-OH-17a-o x a - 1 7 - C = 0
17/3-Ac—17-C=0
17/3-Ac->17-C=0
17/3-Ac->17-C = 0
1
Δ
1
Δ
Δ ; 17/3-Ac — 17a-oxa -17-C=0
9 a - B r - H ; Δ ; 17ß-Ac - 17a-o x a - 1 7 - C = 0
17/3-Ac-*17-C=0
Δ1; 1 7 / 3 - A c -17a -oxa -17 -C=0
Δ ; 17/3-Ac — 17a-oxa -17-C=0
-
17j3-Ac-»17-C=0
17j3-Ac^l7ß-OH
17ß-(20-C=O-21-OH)->17-C=0
17ß-(20-C=O-21-OH)->17ß-OH
R E F .
F-275
E-195
T-996
T-996
T-996
S-890
S-890
L-492
L-492
T-996
T-996
L-492; T-996
T-1005
S-880
S-880
S-880
S-880
TABLE I I I
T r a n s f o r m a t i o n s by G e n u s : CYLINDROCEPHALUM DACTYLIUM
DALDINIA DEBARYOMYCES
TAXONOMY
(Imperfo - Moniliales) (AscOo - Sphaeriales) (AscOo - Endomycetales)
SPECIES
aureum
DACTYLRJM
dendroides
DALDINIA
concentr ia (concentrica)
DEBARYOMYCES
hansenii
SOURCE
ATCC-12720 (QM-610)
NRRL-2574 (QM-508)
NRRL-2575 (QM-513)
QM
FRI
NRRL
SUBSTRATE
21-hydroxy-4 -p regnene-3 ,20-dione propionate
4 -pregnene-3 ,20-d ione
21-hydroxy-4 -p regnene-3 ,20-dione
16a-methyl -4-pr egnene - 3 , 2 0 -dione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
l i a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
17a -hydraxy-4 -p regnene -3 ,20 -dione
21-hydroxy-4 -p regnene-3 ,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
REACTION
17/3-(20-C=O-2 1 - O P r ) -» 1 7 - C = 0
17/3-(20-C=O-21-OPr) -» 17/3-OH
l l a , 1 7 a - d i O H
l l a , 1 7 a - d i O H
l l a , 1 7 a - d i O H
l l a , 1 7 a - d i O H
l l a - O H
17a-OH
l l a , 1 7 a - d i O H
17a-OH
l l a - O H
l l a - O H
l l a , 1 7 a - d i O H
l l a - O H
6j3-OH; l l a - O H
—
-
R E F .
S-880
S-880
D-188
D-188
M-571
D-188
D-189
D-189
D-189
D-189
D-189
D-189
D-189
D-189
S-849
M-587
M-587
M-587
393
394
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by G e n u s : DEMATIACEAE (Family) (Imperf0 - Moniliales)
DEMATIUM (Imperfo - Moniliales) DERMOLOMA (Basidio. - Agaricales)
DIAPORTHE (Asco„ - Sphaeriales) DIDYMELLA (Asco0 - Sphaeriales)
SPECIES
species
DEMATIUM
puliulans
DERMOLOMA
species
DIAPORTHE
numurai
DIDYMELLA
lycopersici
SOURCE
NG
NRRL
AL(F-27)
FRI
IAM
(A-47)
AMCY
ATCC-11847
C
SUBSTRATE
17«, 21 -dihydroxy-4-pregnene -3,20-dione
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
4-pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17o, 21 -dihydroxy-4-pregnene -3,20-dione
11β, 17α, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione (use of dr ied thalli)
17a, 21-dihydr oxy-4-pregnene-3,20-dione
(use of spo res - Ref. S-835, S-836)
2a-f luoro- 17a, 21 -dihydroxy -4 -p regnene -3 ,11 ,20 - t r i one
17/3-hydroxy -4 -andros ten-3 -one
17a-ethinyl-17jS-hydroxy-4-andros ten-3-one
REACTION
20-C=O -> 20/3-OH
—
-
-
6/3,l la-diOH
-
-
2/3-OH
1
Δ
17a-OH-17j3-(20-C=O-21-OH) — 1 7 - C = 0
11a-OH
20-C=O-+ 20j3-OH
1
Δ
1
Δ 1
Δ
R E F .
V-1045
M-587
M-587
M-587
S-825
S-849
S-849
S-849
F-231
V-1048
S-835; S-836; V-1048
S-835; S-836; V-1048
H-401
W-1105
V-1052; W-1096; W-1104
TABLE I I I
Transformat ions by Genus: D I D Y M E L L A
395
SPECIES
lycopers ic i
SOURCE
C
SUBSTRATE
17ß-hydroxy-17ö-methyl -4-andr ei-s ten-3-one
17/3-hydroxy-17a-vinyl-4-andro-s ten-3-one
l - and ros t ene -3 ,17 -d ione
4 -androstene -3 ,17 -dione
p regnane-3 ,20-d ione
17a, 21-dihydr.oxy-5a-pregnane-3 ,11 ,20 - t r ione
5α -1 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21 -dihydroxy-4 -pregnene -3,20-dione
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
d , l - l l ß , 1 7 a , 2 1 - t r i h y d r o x y - 4 -pregnene-3 ,20-d ione
9a - f luo ro - l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
9a - f luoro- l l j3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione 2 1 -aceta te
17a,21-dihydroxy-9/3,11/3-oxido-4-pregnene-3 ,20-d ione 2 1 -aceta te
d, 1-11/3,17a, 21- t r ihydroxy-4-pregnene-3 ,20-d ione 2 1 -t r imethylace ta te
d, 1-11/3,21-dihydroxy-3, 20-d i -ke to -4 -p regnen-18-a i (18 -» 11) hemiace ta i
21 -hyd roxy -4 -p regnene -3 ,11 ,20 -t r ione
17a,21 -dihydroxy-4 -pregnene -3 ,11 ,20 - t r ione
d , l - 1 7 a , 2 1 - d i h y d r o x y - 4 - p r e g -n e n e - 3 , 1 1 , 2 0 - t r i o n e
REACTION
Δ1
1
Δ
4
Δ 1
Δ
Δ 1 ' 4
* V
4
Δ
Δ1
1
Δ
1
Δ
1
Δ
d,l—d-Δ + 1
1
Δ
Δ ; 2 1 - O A c -21-OH
Δ1; 2 1 - O A c -21-OH
d , l ->d-A X + 1
afl^d-Al + 1
1
Δ
1
Δ
d , l ^ d-Δ 1 + 1
R E F .
V-1052; 1 W-1096; W-1104
W-1109
W-1096
W-1096
W-1096
W-1096
W-1096
W-1096
W-1096
V-1052; W-1096
V-1052: W-1096
W-1102
W-1096
V-1052
W-1096
W-1102
V-1055; W-1102
W-1096
V-1052; W-1096
V-1055> W-1102
396
TABLE I I I
T r a n s f o r m a t i o n s by Genus: DIDYMELLA DIDYMOCLADIUM
DIPLODIA
TAXONOMY
(Imperf. (Imperf.
Moniliales) Sphaeropsidales)
SPECIES
lycopers ic i
vodakii
DIDYMOCLADIUM
te rna tum
DIPLODIA
nata lens is
SOURCE
C
CBS
C
AMCY
ATCC-9055
SUBSTRATE
17a-methy l -21-hydroxy-4-preg-n e n e - 3 , l l , 2 0 - t r i o n e 2 1 -aceta te
21-hydroxy-4 ,6 -pregnad iene-3,20-dione 21-aceta te
4, l l - p r egnad iene -3 ,20 -d ione
17a,21 -dihydroxy -4 -pregnene -3,20-dione
3/3, 1 Iß -dihydroxy -5α -pregnan-20-one
3ß-hydroxy -19 -nor-4 -pr egnen -20-one
16a ,17a-ox ido-4-pregnene-3 , 20-dione
4 -andros tene-3 ,17-d ione
A-nor -3 -p regnene-2 ,20-d ione
4-pregnene-3 ,20-d ione
21-hydroxy-4-p regnene-3 ,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
l l / 3 ,17a ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-dione
9a - f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene-3 ,11 ,20- t r ione
17a, 21-d ihydroxy-1 ,4 -p regna-diene-3 ,20-dione
l l j 3 , 1 7 a , 2 1 - t r i h y d r o x y - l , 4 -pregnadiene-3 ,20-d ione
REACTION
1
Δ
Δ1; 21-OAc-> 21-OH
1
Δ
2 0 - C - O - * 20/3-OH
16a-OH
16a-OH
l l a - O H
7a-OH
7a-OH
7a-OH
7a-OH
7a-OH
7a-OH
7a-OH
7a-OH
7a-OH
7a-OH
R E F .
V-1052; W-1096
V-1052; W-1096
V-1052; W-1096
S-836
W-1092
W-1093
P-746
T-997
L-502; L-506; >V-1078
T-997
T-997
T-997; T-998; T-999
T-997
T-997
T-997
T-997
T-997
TABLE I I I
397
T r a n s f o r m a t i o n s by G e n u s : DIPLODIA DIPLODASCUS DOTHICHIZA
TAXONOMY
(Asco. - Endomycetales) (Imperf. - Sphaeropsidales)
SPECIES
nata lensis
tuber icola
DIPLODASCUS
albidus
DOTHICHIZA
ferruginosa
SOURCE
FRI
IAM
FRI
ATCC-11918
SUBSTRATE
17a ,21-d ihydroxy-4-pregnene-3,20-dione
3j3-hydroxy-5-pregnen-20-one
4-pregnene-3 ,20-d ione
7/3-hydroxy-4-pregnene - 3 , 2 0 -dione
17o,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
3 - h y d r o x y - l , 3 , 5 (10) -es t ra t r i en-17-one
17ß-hydroxy-4-andros ten-3-one
4 -andr ostene -3 ,17 -dione
4-pregnene-3 ,20-d ione
1 l a -hydroxy-4 -p regnene -3 ,20 -dione
21-hydroxy-4 -p regnene-3 ,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
REACTION
l l ö - O H
Δ ->Δ ; 3/3-OH - 3 - C = 0 ; 7/3-OH
Δ —Δ ; 3ß-OH - 3 - C = 0 ; 7j3,15/3-diOH
7/3-OH
7/3,15j3-diOH
15j3-OH
7o-OH
20-C=O -> 20/3-OH
-
11/3-OH
llj3-OH
l l ß - O H
l l ß - O H
l l ß - O H
l l ß - O H
11/3-OH
R E F .
S-849
A-28; T-1025
A-28; T-1025
A-28; T-1023; T-1025
A-28; T-1025
A-28; T-1025
A-28; T-1023
A-28
S-849
K-449
K-449
K-449
K-449
K-449
K-449
K-449
398
TABLE I I I TAXONOMY
ECHINODONTIUM (Basidio. - Agaricales) ELSINOE (Asco. - Myriangiales)
T r a n s f o r m a t i o n s by Genus : ENDOMYCES (Asco. - Endomycetaies) ENDOTINIA (Taxonomy Unclear - Prob. ENDOTHIA)
(Asco. -Sphaeriales) ENTOMOPHTHORA (Phyco. - Entomophthorales)
SPECIES
tsugicola
ELSINOE
ampelina
fawcetti
ENDOMYCES
lindneri
ENDOTINIA (probably ENDOTHIA)
pa ra s i t i ca
ENTOMOPHTHORA
coronata
EPICOCCUM
humicola
SOURCE
IAM (2-2)
IAM (2-3)
FRI
TNAES
TNAES
FRI
TNAES
ATCC-10151
ATCC-12722 (QM-1049)
SUBSTRATE
17a ,21-d ihydroxy-4-pregnene-3 , 20-dione
17a ,21-d ihydroxy-4-pregnene-3 , 20-dione
17a ,21-d ihydroxy-4-pregnene-3 , 20-dione
17a ,21-d ihydroxy-4-pregnene-3 , 20-dione
17a, 21-d ihydroxy-4-pregnene-3 , 20-dione
17a ,21-d ihydroxy-4-pregnene-3 , 20-dione
17a, 21-d ihydroxy-4-pregnene-3 , 20-dione
4-pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3 , 20-dione
17/3-hydroxy-4-androsten-3-one
4 -andros tene-3 ,17-d ione
20-hydroxy-5/3-pregnan-3-one
2 0 - hy dr oxy - 5a -pr egnan - 3 - one
3/3-hydroxy-5-pregnen-20-one
REACTION
-
-
~
-
-
-
-
oxidation -products not identified
6-OH; 11α-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
R E F .
S-849
S-849
S-849
S-849
S-849
S-849
S-849
W-1073
W-1073
R-782
R-782
R-782
R-782
R-782
E P I C O C C U M (Imberf. - Moniliales)
TABLE I I 1
Transformat ions by Genus: EPICOCCUM
399
SPECIES
humicola
*
*
neglectum
*
oryzae
1 *
SOURCE
ATCC-12722 (QM-1049)
ATCC-12723 (QM-1070)
ATCC-12724 (QM-1053)
SUBSTRATE
4-pregnene-3 ,20-d ione
17a -hydroxy-4 -p regnene-3 ,20-dione
17a, 21 -dihydr oxy -4 -pr e gnene -3 ,20-dione
17a, 21-dihydr o x y - 1 , 4 - p r e gna-d iene-3 ,20-d ione
4 ,6 -p regnad iene -3 ,20-d ione
17/3-hydroxy-4-androsten-3-one
4 -andr ostene -3 ,17 -dione
20-hydroxy-5/3-pregnan-3-one
20-hydroxy-5a-pregnan-3-one
3/3-hydroxy-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
17a-hydroxy-4-p regnene-3 ,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21-dihydroxy - 1 , 4 - p r egna-d iene-3 ,20-d ione
4 ,6 -pregnadiene -3 ,20-d ione
17/3-hydroxy-4-androsten-3-one
4 -androstene -3 ,17 -dione
20-hydroxy-5a-pregnan-3-one
20-hydroxy-5/3-pregnan-3-one
3/3-hydroxy-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
17a-hydroxy-4-p regnene-3 ,20-dione
17a, 21 -dihydroxy-4-pregnene -3 ,20-dione
6/3 -fluoro -17a -hydroxy - 21 - methyl -4 -p regnene-3 ,20-d ione
REACTION
11/3-OH
11/3-OH
11/3-OH
20-C = O ^ 20/3 -OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
R E F .
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
H-391
TABLE I I I
Transformations by Genus: EPICOCCUM
SPECIES
oryzae
purpurascens
species
yuccae
SOURCE
ATCC-12724 (QM-1053)
FRI
QM-649
ATCC-12725 (QM-284e)
SUBSTRATE
6a -f luor o -1 la, 21 -dihydr oxy -16-mé thy lène -4 -p regnene-3 ,20-dione
17a, 21 -dihydroxy -1 ,4 -pr egna -d iene-3 ,20-d ione
4 ,6 -pregnadiene -3 ,20-dione
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
17/3-hydroxy -4 -andros ten-3 -one
4 -andros tene-3 ,17-d ione
20-hydroxy-5a-pregnan-3-one
20-hydroxy-5j3-pregnan-3-one
4-pregnene-3 ,20-d ione
17a-hydroxy-4-pregnene-3 ,20-dione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
17a, 21-d ihydroxy-1 ,4 -pregna-diene-3 ,20-dione
4 ,6 -pregnadiene -3 ,20-dione
17/3-hydroxy-4-androsten-3-one
4 -androstene -3 ,17 -dione
2 0 - hy dr oxy - 5a-pr e gnan - 3 - one
20-hydroxy-5/3-pregnan-3-one
3/3-hydroxy-5-pregnen-20-one
4-pregnene-3 ,20-d ione
17a-hydroxy-4-pregnene-3 ,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-1 ,4-pr egna- J d iene-3 ,20-dione
4 ,6 -pregnad iene-3 ,20-d ione
REACTION
11/3-OH
11/3-OH
11/3-OH
-
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3 -OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
R E F .
A-7
R-782
R-782
S-849
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
R-782
400
3j3-hydroxy-5-pregnen-20-one
401
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: EPIDERMOPHYTON
EREMASCUS EREMOTHECIUM
ERWINIA ESCHERICHIA
(Imperf. - Moniliales) (Asco. - Endomycetales) (Asco. - Endomycetales) (Schizo. - Eubacteriales) (Schizo. - Eubacteriales)
SPECIES
floccasum
EREMASCUS
albus
EREMOTHECIUM
ashbyii
ERWINIA
aroideae
carotovora
(in mixed cul ture with Mycococcus sp. Ax)
ESCHERICHIA
coli
1 (in mixed cul ture 1 with Mycococcus
sp. Ax)
SOURCE
FRI
NRRL
SQ
FAKU
IFO (3380)
LAM (s t ra in 2 , 6 -Bordet ,Naj iar ATCC-3635)
(s t ra in 7)
(s t ra in 8)
(ML-3)
IFO (3043)
SUBSTRATE
17ö, 21 -dihydroxy-4 -pregnene-3,20-dione
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
• 3ß-hydroxy-5-pregnen-20-one
17ö, 21 -dihydroxy -4 -pregnene -3,20-dione
l l j 3 ,17a ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
17ö, 21-dihydroxy-4-pregnene -3,20-dione
17ö, 21-dihydroxy-4-pregnene -3,20-dione
1 la, 21 -dihydroxy-4 -pregnene -3,20-dione
1 7 Ö , 21-d ihydroxy-4-pregnene-3,20-dione
l l /3 ,17o ,21-d ihydroxy-4-pregnene-3 ,20-di one
REACTION
-
-
-
-
Δ -»Δ ; 3/3-OH - 3 - C = 0
—
1
Δ
-
2/3-OH
11α-ΟΗ;11β-ΟΗ
2/3-OH
—
1
Δ
R E F .
S-849
M-587
M-587
M-587
P-710
S-849
1-428
1-428
S-849
S-849
S-849
S-849
1-428
1-428
402
T r a n s f o r m a t i o n s by Genus:
TABLE I I I
ESCHERICHIA EUGLENA
FLAVOBACTERIUM
TAXONOMY
(Phytomastigina - Euglenoidina) (Schizo. - Eubacter ia les)
SPECIES
coli
freundii
EUGLENA (Protozoa)
grac i l i s va r . bac i l la r i s
FLAVOBACTERIUM
androstenedionicum
SOURCE
IMJ
NG
NIH
NG
NG
SUBSTRATE
3ß-hydroxy-5-andros ten-17-one
3α, 7a-dihydroxy-5/3-cholanic acid
3α, 7α, 12a-trihydroxy-5/3-cholanic acid
5 -cholesten -3/3 -ol (sole carbon source)
24/3-methyl -5 ,7 ,22-choles ta-triene-3/3-01
3a-hydroxy-5/3-cholanic acid (preparat ion of 3-hydroxy bile acid dehydrogenase -grown in p re sence of cholic acid»)
4 -andros tene-3 ,17-d ione
5-androstene-3/3,17/3-diol
3/3-hydroxy-5-androsten -17-one
REACTION
5 4
Δ -»Δ ; 3]3-OH - 3 - C = 0
7a-OH-»7-C = 0
3a-OH->3-C = 0 ; 7a-OH-+7-C=0; 12a-OH -> 1 2 - C = 0
7 a - O H ^ 7 - C = 0
utilization
utilization
3 a - O H - > 3 - C = 0
6 - C = 0
1 7 - C = 0 -17/3-OH
Δ 4 - 5 α - Η ; 3-C=0— 3a-OH
Δ 4 - 5 α - Η ; 3-C=0—3a-OH; 17-C=0-*17/3-OH
Δ*—Δ*; 3/3-OH - 3 - C = 0 ; 17/3-OH -* 1 7 - C = 0
Δ 5 - Δ 4 ; 3/3-OH - 3 - C = 0
R E F .
S-822
N-675
S-799
N-675
S-914; T-1030
C-140; M-595; S-793c
S-793c
H-352; H-353
G-322
G-322
G-322
G-322
E-219
E-219
TABLE I I I
Transformat ions by Genus: F L A V O B A C T E R I U M
403
SPECIES
androstenedionicum
(variant i)
aquatile
aurant iacum
buccalis
carbonil icum
dehydrogenans var . hydrolyticum
SOURCE
NG
RIND (36-1)
NRRL
RIND (38-3)
NG
ATCC-13930 (WC-130)
SUBSTRATE
3/3,17a-dihydroxy-5-pregnen-20-one
5-andros tene-3ß , 17/3-diol
3 /3 ,17a ,21- t r ihydroxy-5-pregnen-20-one
3 /3 ,17a ,21- t r ihydroxy-5-pregnen-20-one 21-aceta te
3 /3 ,17a ,21- t r ihydroxy-5-pregnen-20-one 3 ,21-d iace ta te
3 /3 ,17a ,21- t r ihydroxy-5-pregnen-20-one 3-formate 21-aceta te
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
3 /3 ,17a ,21- t r ihydroxy-5-pregnen-20-one
3/3,17a, 21 - t r ihydroxy -5 -pr egnen -20-one 21-ace ta te
3 /3 ,17a ,21- t r ihydroxy-5-pregnen-20-one 3 ,21-d iace ta te
3 /3 ,17a ,21- t r ihydroxy-5-pregnen-20-one 3-formate 21-ace ta te
5/3-androstene-3/3,17/3-dioI
5 ,9-cyclo - l -androstene-11/3,17/3-diol -3-one 11-aceta te 17-propionate
16 ,16-di f luoro-5-andros ten-3/3-ol-17-one
1 6 , 1 6 - d i f l u o r o - 3 - h y d r o x y - l , 3 , 5 (10) -es t ra t r ien-17-one 3-methyl ether
REACTION
Δ —Δ ; 3/3-OH — 3 - C = 0
Δ5->Δ4; 3/3-OH -» 3-C = 0 ; 1 7 / 3 - O H -1 7 - C = 0
-
21-OAc-*21-OH
-
3-formate —» 3j3-OH
-
-
-5 4
Δ ->Δ ; 3/3-OH ->3-C=0
Δ -*Δ ; 3/3-OH ->3-C=0; 2 1 -O A c - 2 1 - O H
Δ -»Δ ; 3/3-OAc ^ 3 - C = 0
-
Δ5->Δ4; 3/3-OH —3-C=0;17/3-OH—17-C = 0
Δ5->Δ4; 3/3-OH -» 3-C = 0
Δ -11/3-OAc — 1/3,11/3-oxide
1 7 - C = 0 ^ 17a -OH; 3/3-OH ^ 3 - C = 0 ; Δ 5 - Δ 4
1*7-C=0 -17a-OH
R E F .
E-222
E-220
P-744
P-744
P-744
P-744
M-587
M-587
M-587
P-744
P-744
P-744
P-744
M-592
M-592
R-777
R-774
R-774
404
TABLE I I I
Transformat ions by Genus: FLAVOBACTERIUM
SPECIES
dehydrogenans var . hydrolyticum
SOURCE
ATCC-13930 (WC-130)
SUBSTRATE
16-diazo-3ß-hydroxy-5-andros ten -17-one
17a-ethinyl-l l /3,17/3-dihydroxy-4 ,6 -andros tad ien-3 -one diacetate
1 la - ethiny 1 -11 j3,1 7/3 -dihydroxy -l , 4 , 6 - a n d r o s t a t r i e n - 3 - o n e diacetate
11/3, 17/3-dihydroxy-17a-methyl-1,4,6 -andr os ta t r ien - 3 -one diacetate
3/3-hydroxy -16 -méthylène - 5 -andros ten-17-one
5-pregnene-3/3,20a-diol
5-pregnene-3/3, 20/3-diol
7a-methyl-5-pregnene-3/3 , 7/3, 20/3-triol
3/3-hydroxy -D-nor -5 -pregnen -20-one
1 la - ch loro- 3/3-hydroxy -5 -pregnen -20-one aceta te
1 ß , 3 /3-dihydr oxy -5 -pregnen -20-one
3 j3 ,17o,21- t r ihydroxy-5-pregnen-20-one 21-aceta te
3 /3 ,17a ,21- t r ihydroxy-5-pregnen-20-one 3 ,21-d iace ta te
3/3-hydroxy-16,16-dimethyl-5-pregnen-20-one
3/3-hydroxy-16/3-methyl-16a, 17a-oxido-5-pregnen-20-one
3/3 ,17a,21- t r ihydroxy-16a-methyl -5-pregnen-20-one 21-aceta te
3β, 17α, 21 - t r ihydroxy-16ß- methyl -5-pregnen-20-one 3 , 2 1 -diacetate
REACTION
3 ß - O H ^ 3 - C = 0 ; Δ3-+Δ4
11/3,17/3-diOAc ->ll/3,17/3-diOH
11/3-OAc -» ll/3-OH;17/3-OAc->17/3-OH
11/3-OAc—11/3-OH; 17/3-OAc -> 17/3-OH
3j3-OH-+3-C = 0 : Δ —*Δ
Δ —Δ ; 3/3-OH ->3-C = 0
Δ ' - Δ 4 ; 3/3-OH ->3-C = Oj 20/3-O H ^ 2 0 - C = O
Δ —Δ; 3/3-OH^ 3-C = O;20/3-OH - 2 0 - C = O
Δ -»Δ ; 3/3-OH ^ 3 - C = 0
5 4 Δ -»Δ ; 3/3-OAc - 3 - C = 0
Δ —Δ ; 3/3-OH - 3 - C = : 0
3ß-OH-»3-C = 0 ; A5->A4;21-OAc —21-OH
3 ß - O A c - 3 - C = 0 ; Δ -*Δ4; 21-OAc ->21-OH
3/3-OH-»3-C=0; Δ5->Δ4
3ß-OH-»3-C=0: Α^ Λ 4
Δ —»Δ 3/3-OH-3-C = 0 ; Δ5-»Δ4; 21-OAc -»21-OH
3/3-OAc-^3-C = 0 ; Δ5-+Δ4; 21-OAc -»21 -OH
R E F .
R-763
G-304
G-304
G-305
B-76
N-693
N-693
R-776
R-763
R-761
N-688; N-689
H-378
H-378
S-837
S-837
C-109; 1-421; 1-422
C-109; 1-421; 1-422
TABLE I I I
Transformat ions by Genus: FLAVOBACTERIUM
405
SPECIES
dehydrogenans
SOURCE
ATCC-13930 (WC-130)
SUBSTRATE
3/3 ,17a,21- t r ihydroxy-16-methylene-5-pregnen-20-one 3 ,21-d iace ta te
1/3,3/3,17a, 21 - t e t r ahydroxy-5 -pregnen-20-one 1 , 3 , 2 1 -t r i ace t a t e
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - 5 , 9 -cyc lo - l -p regnene -3 ,20 -d ione 11/3,21-diacetate
l l / 3 , 17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione 11/3,21-diacetate
21-hydroxy-17j3,20a-oxido-16-ox imino -4 -p regnene -3 ,11 -dione aceta te
9 a - b r o m o - l l / 3 - c h l o r o - 1 7 a , 2 1 -d ihydroxy-5-p regnene-3 ,20-dione 21-aceta te
9 a - b r o m o - l l / 3 - f l u o r o - 1 7 a , 2 1 -d ihydroxy-5-p regnene-3 ,20-dione 21-aceta te
l l / 3 -b romo-9a - f l uo ro -17a ,21 -d ihydroxy-5 -p regnene-3 ,20-dione 21-aceta te
l l / 3 - ch lo ro -9a - f luo ro -17a ,21 -d ihydroxy-5-p regnene-3 ,20-dione 21-ace ta te
9a , l l /3 -d ich loro-17a ,21-d ihydroxy -5 -p regnene -3 ,20 -d i one 21-aceta te
9a , l l /3-d i f luoro-17a ,21-dihydroxy -5 -pregnene-3 ,20-d ione 21-aceta te
9a - ch lo ro - l l / 3 - f l uo ro -17a ,21 -dihydroxy-2o-iïB t h y l - 5 -p regnene-3 ,20-d ione 2 1 -aceta te
9a, l l /3 -d ich loro-16a-e thyl -17a , 21 -dihydroxy - 5 -pregnene -3,20-dione 21-ace ta te
9a , l l /3 -d ich loro-17a ,21-d ihydroxy -6 -methy l -5 -pregnene - 3 , 2 0 -dione 21-aceta te
REACTION
5 4
Δ —Δ ; 3/3-OAc - 3 - C = 0 ; 2 1 -OAc—21-OH
l/3-OAc-l/3-OH; 21-OAc—21-OH; 3 /3 -OAc-3-C=0; Δ 5 - Δ 4
11/3,21-diOAc— 11/3,21-diOH; Δ ^ Ι Ι β - Ο Η - * 1/3,11/3-oxide
l l / 3 - O A c - l l / 3 -OH; 21-OAc -21-OH
21-OAc -21-OH
21-OAc—21-OH
21-OAc—21-OH
21-OAc—21-OH
21-OAc—21-OH
21 -OAc-21 -OH
21-OAc-21 -OH
21 -OAc-21 -OH
21-OAc—21-OH
2 1 - O A c - 2 1 - O H
R E F .
T-981
N-689
G-292; R-777
C-129
N-686
N-691
N-691
N-691
N-691
N-691
N-691
N-691
N-691
N-691
406
TABLE I I I
Transformat ions by Genus: FLAVOBACTERIUM
SPECIES
dehydrogenans
SOURCE
ATCC-13930 (WC-130)
SUBSTRATE
9a, l l /3-dichloro-17a, 21-dihydroxy -2a -me thy l -5 -p regnene -3 ,20 -dione 21-aceta te
9a, l l ß - d i c h l o r o - 1 6 a , 17<*,21-t r i hyd roxy-5 -p regnene -3 ,20 -dione 21-aceta te
9a, l l /3-dichloro-21-hydroxy-16a, 17a-isopropylidenedioxy-5-pregnene-3 ,20-d ione aceta te
9a, l l /3-dif luoro-17a, 21-dihydroxy -2a -me thy l -5 -p r egnene -3 ,20 -dione 21-aceta te
9a-chloro- l l /3- f luoro-21-hydroxy -2a-methyl -16a , 17a- i so -propyl idenedioxy-5-pregnene-3,20-dione aceta te
9a-chloro- l l i3- f Iuoro-16a , 17a, 21 - t r ihydroxy-2a -me thy l -5 -pregnene-3 ,20-d ione 2 1 -aceta te
3ß, 16a-dihydroxy-17/3-methyl-18 -no r -5 ,13 -17a -p regna -dien-20-one
3/3,16/3-dihydroxy-17/3-methyl-18-nor_-5,13-17a-pregna-dien-20-one
21-hydroxy-17a-methy l -1 ,4 -pregnadiene -3 ,20 -dione aceta te
11/3,17a-dihydroxy-21-mercapto-l a 4 -p regnad iene -3 ,20 -d ione 21 -aceta te
11/3,21-dihydroxy-17a-methyl-1,4 -pregnadiene -3 ,20-dione 21-aceta te
9a - f luoro- l l /3 ,17a-d ihydroxy-21-mer cap to-1 ,4-pregnadiene -3,20-dione 21-aceta te
6 /3-bromo-l l /3 ,17a,21- t r ihydroxy -1 ,4 -pregnadiene -3 ,20-dione t r i ace ta t e
REACTION
21-OAc-+21-OH
21-OAc^21-OH
21-OAc—21-OH
21-OAc-^21-OH
21-OAc—21-OH
21-OAc—21-OH
3/3-OH^3-C=0; Δ5->Δ4
3/3-OH-»3-C=0; Δ5-*5ξ-Η
3 / 3 - 0 H ^ 3 - C = 0 : Λ 5 A 4
Δ—* Δ 3/3-OH-+3-C = 0 ; Δ 5 - 54-H
21-OAc-^21-OH
21-SAc-»21-SH
21-OAc^21-OH
21-SAc^21-SH
l l / 3 , 1 7 a , 2 1 -triOAc—11/3, 17a ,21- t r iOH
R E F .
N-691
N-691
N-691
N-691
N-691
N-691
S-839
S-839
S-839
S-839
H-377
N-685
H-377
N-685
N-690
TABLE I I I
T ransformat ions by Genus: F L A V O B A C T E R I U M
407
SPECIES
dehydrogenans
SOURCE
ATCC-13930 (WC-130)
SUBSTRATE
9a-fluoro-6£, 11/3,17a, 21 -tetra-hydroxy -1,4 -pregnadiene -3,20-dione tetraacetate
17a-hydr oxy-21-mer capto-1,4-pregnadiene-3,11,20-trione 21-acetate
9a-fluoro-17a-hydroxy-21-mer capto -1,4 -pr egnadiene -3,11,20-trione 21-acetate
9a-fluoro-6£,17a,21-trihydroxy-1,4-pregnadiene-3,11,20-trione 6,21-diacetate
ll/3,17a,21-trihydroxy-l,5-pregnadiene-3,20-dione 21-acetate
11β, 17α, 21 -trihydroxy-1,5-pregnadiene-3,20-dione triacetate
9a-bromo-ll/3-chloro- 17a, 21-dihydroxy -1,5 -pr egnadiene -3,20-dione 21-acetate
ll/3-bromo-9a-chloro-17a,21-dihydr oxy -1,5 -pr e gnadiene -3,20-dione 21-acetate
9a-bromo-llj3-fluoro-17a, 21-dihydroxy -1,5 -pre gnadiene -3,20-dione 21-acetate
ll/3-bromo-9a-fluoro-17a, 21-dihydroxy-1,5-pr egnadiene-3,20-dione 21-acetate
9a, 11/3-dibromo- 17a, 21-dihydroxy -1,5 -pregnadiene -3,20-dione 21-acetate
9a-chloro-ll/3-fluoro-17a, 21-dihydroxy - 1 , 5-pregnadiene -3,20-dione 21-acetate
llj3-chloro-9a-fluoro-17a,21-dihy dr oxy -1,5 -pre gnadiene -3,20-dione 21-acetate
ll/3-chloro-9a-iodo-17a, 21-dihydroxy-1,5-pre gnadiene-3,20-dione 21-acetate
REACTION
6ξ,11/3,17α,21-tetraOAc^ 6ξ, 11/3,17α, 21-tetraOH
21-SAc-*21-SH
21-SAc^21-SH
6£-OAc-6£-OH; 21-OAc^21-OH
21-OAc->21-OH
11/3,17a,21-triOAc^ll/3,17a, 21-triOH
21-OAc^21-OH
21-OAc—21-OH
21-OAc->21-OH
21-OAc-*21-OH
21-OAc^21-OH
21-OAc^21-OH
21-OAc—21-OH
21-OAc->21-OH
REF.
G-309
N-685
N-685
G-309
N-690
N-690
N-691
N-691
N-691
N-691
N-691
N-691
N-691
N-691
408
TABLE I I I
Transformat ions by Genus: FLAVOBACTERIUM
SPECIES
dehydrogenans
SOURCE
ATCC-13930 (WC-130)
SUBSTRATE
9a , l l / 3 -d i ch lo ro -17a ,21 -d i -vydroxy -1 ,5 -pregnadiene -3,20-dione 21-aceta te
16a-e thyl - l l /3 ,17a ,21- t r ihydroxy -1 ,5 -pregnadiene - 3 , 2 0 -dione 21-aceta te
l l /3- f luoro-17a ,21-dihydroxy-9a-iodo-1 ,5 -p regnad iene-3 ,20-dione 21-aceta te
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy - 1 , 5 -pregnadiene -3 ,20-dione t r i ace ta te
9ö, l l /3-dif luoro-17ö,21-dihydroxy -1 ,5 -p regnad iene-3 ,20-d ione 21-aceta te
11/3,17o,21-tr ihydroxy-16û-methyl -1 ,5 -pregnadiene - 3 , 2 0 -dione 21-aceta te
11/3,17α, 21-trihydroxy-16/3-methy l -1 ,5 -pregnadiene - 3 , 2 0 -dione 21-aceta te
9o-bromo-11/3-chlor o - l 6α-ethyl-17α, 21-d ihydroxy-1 ,5 -pregna-d iene-3 ,20-d ione 21-aceta te
9a-bromo- l l /3 -ch loro-21-hydroxy -16α, 17a-isopropylidenedioxy-1,5 -pregnadiene -3 ,2 0-dione 21-aceta te
9a -b romo-16a-e thy l - l l / 3 ,17a , 21 -t r ihydroxy-1 ,5 -p regnad iene -3,20-dione 21-aceta te
9a -b romo- l l / 3 - f l uo ro -17a ,21 -dihydroxy-1 ,5-pregnadiene -3,20-dione 21-aceta te
9a-bromo- l l /3 - f luoro-21-hydroxy-16a, 17a-isopropylidenedioxy-1,5 -pregnadiene -3 ,20-dione 21-aceta te
9α-bromo-11/3 ,17a ,21- t r ihydroxy-16a-methy l -1 ,5 -p regnad iene-3,20-dione 21-aceta te
9a -b romo- l l / 3 ,17a ,21 - t r i hyd roxy-16β -methyl -1 ,5 -pregnadiene -3,20-dione 21-aceta te
6 , 9 a - d i b r o m o - l l ß - f l u o r o - 1 7 a , 21 -d ihydroxy-1 ,5 -pregnadiene -3 ,20-dione 21-aceta te
REACTION
21-OAc->21-OH
21-OAc->21-OH
21-OAc-+21-OH
l l / 3 , 1 7 a , 2 1 - t r i -OAc-*ll/3,17a, 21-tr iOH
21-OAc^21-OH
21-OAc-21-OH
21-OAc^21-OH
21-OAc—21-OH
21-OAc-*21-OH
21-OAc-21-OH
21-OAc-*21-OH
21-OAc-21-OH
21-OAc-*21-OH
21-OAc-*21-OH
21-OAc-21-OH
R E F .
N-691
N-690; N-692
N-691
N-690
N-691
N-690; N-692
N-690; N-692
N-691
N-691
N-690; N-692
N-691
N-691
N-690; N-692
N-690; N-692
N-691
TABLE I I I
Transformat ions by Genus: FLAVOSACTERIUM
409
SPECIES
dehydrogenans
SOURCE
ATCC-13930 (WC-130)
SUBSTRATE
9 a , l l / 3 - d i b r o m o - 1 7 a , 2 1 - d i -hydroxy-6-methy 1-i, 5 -pregna-d iene-3 ,20-d ione 21-aceta te
9 a , l l / 3 - d i b r o m o - 1 7 a , 2 1 - d i -hydroxy-16/3-methyl- l , 5-pregnadiene-3 ,20-d ione 21-aceta te
9α, l l ß - d i b r o m o - 1 7 a , 21 -d i -hydroxy-16α-methy 1-1, 5-pregnadiene-3 ,20-d ione 21 -aceta te
9a-chloro- l l j3- f luoro-16a , 17a, 21 - t r i hyd roxy-1 ,5 -p regna -d iene-3 ,20-d ione 21-aceta te
9a -ch lo ro - l l / 3 - f l uo ro -17a ,21 -d ihydroxy-16/3-methyl - l ,5 -pregnadiene-3 ,20-d ione 21-ace ta te
9 a - c h l o r o - l l ß - f l u o r o - 1 7 a , 2 1 -dihydr oxy - 6 - methy 1-1,5-pregnadiene -3 ,20-dione 21-aceta te
9a-chloro- l l /3- f luoro-21-hydroxy-16a, 17a-isopropylidenedioxy-1,5 -pregnadiene -3 ,20-dione aceta te
9a -ch loro- l l j3 ,17a ,21- t r ihydroxy-1 6 a - m e t h y l - l , 5-pregnadiene -3,20-dione 21-aceta te
9a -ch lo ro - l l j3 ,17a , 21- t r ihydroxy-16j3 - methyl - 1 , 5 -pre gnadiene -3,20-dione 21-ace ta te
9 a , l l j 3 - d i c h l o r o - 1 6 a , 1 7 a , 2 1 - t r i -hydroxy-1 ,5-pregnadiene -3,20-dione 21-ace ta te
9a , l l /3 -d ich loro-17a ,21-d ihydroxy - 1 6 a - m e t h y l - l , 5-pregnadiene -3,20-dione 21-ace ta te
9a , l l /3 -d ich lo ro-21-hydroxy-16a , 17a - isopr opylidenedioxy - 1 , 5 -p r e gnadiene -3 ,20 - dione ace ta te
9a , l l /3 -d ich loro-17a ,21-d ihydroxy -16j3-methyl- l , 5-pregnadiene -3 ,20-dione 21-aceta te
REACTION
21-OAc—21-OH
21-OAc^21-OH
21-OAC-21-OH
21-OAc—21-OH
21-OAC-21-OH
21-OAc-21-OH
21-OAc^21-OH
21-OAc—21-OH
21-OAc->21-OH
21 -OAc-21 -OH
21-OAc—21-OH
21-OAc-*21-OH
21-OAC-21-OH
R E F .
N-691
N-691
N-691
N-691
N-691
N-691
N-691
N-690; N-692
N-690; N-692
N-691
N-691
N-691
N-691
410
TABLE I I I
Transformations by Genus: FLAVOBACTERIUM
SPECIES
dehydrogenans
SOURCE
ATCC-13930 (WC-130)
SUBSTRATE
9a , l l /3-d ichloro-17a ,21-dihydroxy -6-methy 1-1,5-pregnadiene-3,20-dione 21-aceta te
16a -e thy l -9a - f luo ro - l l / 3 ,17a ,21 -t r ihydroxy - 1 , 5 -pr egnadiene -3,20-dione 21-aceta te
11/3- fluor o - 21 - hy dr oxy - 9a - iodo -16a, 17a-isopropylidenedioxy-1,5 -pr egnadiene -3 ,20-dione 21-aceta te
l l /3- f luoro-17a,21-dihydroxy-9a-iodo-6 -me thy l -1 , 5-pregna-diene-3 ,20-dione 21 -ace t a t e
l l /3- f luoro-17a ,21-dihydroxy-9a-iodo-16a-methy l -1 , 5-pregna-diene-3 ,20-dione 21-aceta te
l l /3- f luoro-17a ,21-dihydroxy-9a-iodo-16/3-methy l - l ,5 -pregna-diene-3 ,20-dione 21-aceta te
9a-fluoro-11/3,17a, 21- t r ihydroxy-16a-methy 1-1, 5-pr egnadiene -3,20-dione 21-aceta te
9a- f luoro- l l /3 ,17a , 21- t r ihydroxy-16/3-methyl - 1 , 5 -pr egnadiene -3,20-dione 21-aceta te
9a, 11 ß -dif luor o -17a, 21 -dihydr oxy-16a - methyl -1 ,5 -pregnadiene -3,20-dione 21-aceta te
9a , l lß -d i f luoro-17a ,21-d ihydroxy-16/3-methy 1-1, 5-pregnadiene 3,20-dione 21-aceta te
9a-bromo- l l /3 - f luoro-17a , 21 -d i -hydr oxy-6 ,16a -d ime thy l -1 , 5-pregnadiene-3 ,20-d ione 2 1 -aceta te
9a-bromo- l l /3 - f luoro-17a , 21 - d i -hydr oxy-6,16/3-dimethyl- l , 5-pregnadiene-3 ,20-d ione 2 1 -aceta te
9a , l l /3 -d ibromo-17a ,21-d ihydroxy-6 ,16a -d ime thy l -1 ,5 -p r egna-d iene-3 ,20-dione 21-aceta te
9a , l l /3 -d ibromo-17a ,21-d ihydroxy-6,16/3-dimethyl- l , 5 -pregna-diene-3 ,20-dione 21-aceta te
REACTION
21-OAc^21-OH
21-OAc—21-OH
21-OAc->21-OH
21-OAc^21-OH
21-OAc^21-OH
21-OAc-21-OH
21-OAc—21-OH
21-OAc—21-OH
21-OAc—21-OH
21-OAc-»21-OH
21-OAc^21-OH
21-OAc—21-OH
21-OAc-*21-OH
21-OAc^21-OH
R E F .
N-691
N- 690; N-692
N-691
N-691
N-691
N-691
N-690; N-692
N-690; N-692
N-691
N-691
N-691
N-691
N-691
N-691
TABLE I I I
Transformat ions by Genus: FLAVOBACTERIUM
411
SPECIES
dehydrogenans
SOURCE
ATCC-13930 (WC-130)
SUBSTRATE
9a,ll/3-dichloro-16a,17a,21-tri-hydroxy-6-methyl-l, 5-pregna-diene-3,20-dione 21-acetate
9a,ll/3-dichloro-17a,21-di-hydroxy-6,16a-dimethyl-l,5-pr egnadiene-3, 20-dione 21-acetate
9a,ll/3-dichloro-17a,21-dihydroxy -6,16/3-dimethyl-l,5-pregna-diene-3,20-dione 21-acetate
9a-chloro-ll/3-fluoro-16a, 17α , 21-trihydroxy-6-methyl-l,5-pr egnadiene -3,20-dione 21-acetate
9o-chloro-llß-fluor 0-21-hydroxy-16a, 17a-isopropylidenedioxy-6-methyl-l, 5-pregnadiene -3,20-dione acetate
9a,ll/3-difluoro-17a,21-dihydroxy -6,16a-dimethyl-l,5-pregna-diene-3,20-dione 21-acetate
9a, 11/3 -dif luoro -17a, 21 -dihydr oxy -6,16/3-dimethyl-l, 5-pr egna-diene-3,20-dione 21-acetate
17a,21-dihydroxy-l, 5-pregna-diene-3,11,20-trione 21-acetate
17a,21-dihydroxy-l, 5-pregna-diene-3,ll,20-trione 21-isobutyrate
9a-bromo-17a,21-dihydroxy-l,5-pr egnadiene-3,11,20-trione 21-acetate
16a-n-butyl-17a,21-dihydroxy-1,5 -pr egnadiene -3,11,20-trione 21-acetate
16/3-n-butyl-17a, 21-dihydroxy-1, 5-pregnadiene-3,11,20-trione 21-acetate
9a-chloro-17a, 21-dihydroxy-1,5-pre gnadiene -3,11,20-tr ione 21-acetate
16a-ethyl-17a,21-dihydroxy-l,5-pregnadiene-3,ll,20-trione 21-acetate
REACTION
21-OAC-21-OH
21-OAc^21-OH
21-OAc^21-OH
21-OAc-21-OH
21-OAc->21-OH
21-OAc^21-OH
21-OAc^21-OH
21-OAc—21-OH
21-O-i-Bu — 21-OH
21-OAc—21-OH
21-OAc-»21-OH
21-OAc-21-OH
21-OAc—21-OH
21-OAc^21-OH
REF.
N-691
N-691
N-691
N-691
N-691
N-691
N-691
N-690
N-690
N-690
N-690; N-692
N-690; N-692
N-690
N-690; N-692
412
TABLE I I I
Transformat ions by Genus: FLAVOBACTERIUM
SPECIES
dehydrogenans
L
SOURCE
ATCC-13930 (WC-130)
EM
SUBSTRATE
9a-f luoro-17a, 21-dihydr o x y - 1 , 5 -p regnad iene -3 ,11 ,20 - t r ione 21-aceta te
1 7α, 21 -dihydroxy -16a - methyl -1,5 -pregnadiene - 3 , 1 1 , 2 0 -t r ione 21-aceta te
17α, 21 -dihydroxy-16/3- methyl -1,5 -pregnadiene - 3 , 1 1 , 2 0 -t r ione 21-aceta te
9 a - b r o m o - 1 6 a - e t h y l - 1 7 a , 2 1 -dihydr oxy - 1 , 5 -pregnadiene -3 ,11 ,20- t r ione 21-aceta te
9a -bromo-17a ,21-d ihydroxy-1 6 a - m e t h y l - l , 5-pregnadiene -3 ,11 ,20 - t r ione 21-aceta te
9a -bromo-17a ,21-d ihydroxy-16j3-methyl-l , 5 -pregnadiene -3 ,11 ,20- t r ione 21-aceta te
16a -e thy l -9a - f luoro -17a ,21-dihydr oxy-1 ,5-pregnadiene -3 ,11 ,20- t r ione 21-aceta te
9α-fluor o -17α, 21-dihydr oxy -16α-methy l -1 ,5 -pregnadiene -3 ,11 ,20- t r ione 21-aceta te
9a-f luoro-17a, 21 -dihydroxy-16ß-methyl -1 ,5 -pregnadiene -3 ,11 ,20- t r ione 21-ace ta te
9 a - f l u o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 - t e t r a -h y d r o x y - l , 4 , 6 - p r e g n a t r i e n e -3,20-dione 16,21-diace ta te
l l j 3 , 1 7 a , 2 1 - t r i h y d r o x y - l , 4 , 6 -p regna t r i ene -3 ,20-d ione 11-formate 21-aceta te
3/3-hydroxy-16-méthylène-5-androsten -17-one
3/3,17/3-dihydr oxy-17α-methyl-16-méthylène-5-andros tene
3/3-hydroxy-pyrazolo-[4 . 3 : 16 .17]-5-andros tene
1
3/3, l ] j3- dihydr oxy -Δ 2 - isoxazol ino-[4 .5 1 :16„17]-5-andros tene
3/3,17a, 21 - t r ihydroxy -16-méthylène-5-pregnen-20-one 3 ,21-diaceta te
REACTION
21-OAc—21-OH
21-OAC-21-OH
21-OAc-21-OH
21-OAc-21-OH
21-OAc-*21-OH
21-OAc—21-OH
21-OAc-21-OH
21-OAc-21 -OH
21-OAc->21-OH
16a-OAc -» 16a-OH; 2 1 -O A c - 2 1 - O H
11-formate —» l l /3-OH;21-OAc - 2 1 -OH
3/3-OH->3-C=0; Δ 5 - Δ 4
3 /3 -OH-3-C=0; Δ5—Δ4
3 /3 -OH-3-C=0; Δ 5 - Δ 4
3 /3 -OH-3-C=0: Α ^ Λ 4
Δ —*Δ 3/3-OAc—3-C=0; 21-OAc-*21-OH: Δ —»Δ
R E F .
N-690
N-690; N-692
N-690; N-692
N-690; N-692
N-690; N-692
N-690; N-692
N-690; N-692
N-690; N-692
N-690; N-692
G-299
G-302
B-76
B-76
B-76
B-76
M-558
T r a n s f o r m a t i o n s by Genus:
SPECIES
dehydrogenans
f lavescens
1 (in mixed cul ture with Mycococcus sp. Ax)
flavotennae
1 fulvum
SOURCE
NG (see genus Micrococcus)
IFO (3085)
RIND (37-3)
NG
RIND (39-2)
SUBSTRATE
l ,3 ,5 (10) -es t r a t r i ene -3 ,17 /3 -d io l
5a-androstane-3/3,17/3-diol
5-androstene-3/3,17/3-diol
1 la -ethinyl - 5 -andr ostene - 3/3, 17/3-diol
3ß-hydroxy - 5 -andr osten -17 -one
3/3-hydroxy-5-pregnen-20-one
5-cholesten-3/3-ol
3/3-hydroxy-27-nor-5-choles ten-25-one
11/3,17α, 21 - t r i hyd roxy-4 -p reg -nene -3 ,20-dione
3 /3 ,17a ,21- t r ihydroxy-5-pregnen-20-one
3 /3 ,17a ,21- t r ihydroxy-5-pregnen-20-one 21-ace ta te
3 /3 ,17a ,21- t r ihydroxy-5-pregnen-20-one 3-formate 21-ace ta te
3/3, 17α,21 - t r ihydroxy-5-p regnen-20-one 3 ,21-d iace ta te
5-cholesten-3/3-01 (effect of nutr ients)
3/3,17a, 21- t r ihydr oxy-5-pr egnen-20-one
3/3,17a, 21- t r ihydr oxy-5-pr egnen-20-one 21-ace ta te
REACTION
17/3-OH -> 1 7 - C = 0
3 /3-OH^3-C=0; 17/3-OH — 1 7 - C = 0
3/3-OH—3-C=0; Δ 5 - Δ 4
3/3-OH—3-C = 0 ; Δ5->Δ4
3 ß - O H - 3 - C = 0 ; Δ 5 - Δ 4
3/3-ΟΗ—3-C=0; Α^ A 4
Δ —>Δ
utilization
3 /3 -OH-3-C=0; A 5 A 4
Δ —*Δ
-
1
Δ
-
21-OAc->21-OH
3-OFo->3-OH
-
degradation
Δ ^ Δ 4 ; 3/3-OH-> 3 - C = 0
Δ -»Δ ; 3/3-ΟΗ— 3 - C = 0
R E F .
A-15; A-16; E-216
A-15; A-16
A-15; A-16; E-217
A-15; A-16; E-215
A-15; A-16; A-17; E-214
A-15; A-16; E-214
E-214
M-595
A-15; A-16; E-214
1-428
1-428
P-744
P-744
P-744
P-744
A-19
P-744
P-744
TABLE I I I
FLAVOBACTERIUM
413
414
TABLE I I I
Transformat ions by Genus: FLAVOBACTERIUM
SPECIES
fulvum
helvoium ( Nomen confusum -see Corynebacter ium helvoium and C. mediolanum)
mar i s
sewanense *
species
SOURCE
RIND (39-2)
SCH
NG
NG
ATCC-13552
NG (AC-5)
RIND (35-1)
SUBSTRATE
3/3 ,17a,21- t r ihydroxy-5-pregnen-20-one 3-formate 21-aceta te
3 /3 ,17a,21- t r ihydroxy-5-pregnen-20-one 3 ,21-d iace ta te
3/3,21-dihydroxy-5-pregnen-20-one 21-aceta te
5-cholesten-3j3-ol
Digitonin
17j3-hydroxy-17a-methyl-4-andros ten-3-one
4 -p regnene-3 ,20 -dione
21-hydroxy-4-p regnene-3 ,20-dione
17o^21-dihydroxy-4-pregnene-3,20-aione
l l ß , 1 7 a , 2 1 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-dione
9ö-f luoro- l l /3 , 17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
17a, 21 -dihydroxy-4-pregnene -3 ,11 ,20- t r ione
5-cholesten-3j3-ol (sole carbon source - effect of nutr ients)
3 /3 ,17a ,21- t r ihydroxy-5-preg-nen-20-one
3/3, 17a ,21- t r ihydroxy-5 -p reg-nen-20-one 21-ace ta te
3 /3 ,17a ,21- t r ihydroxy-5-preg-nen-20-one 3-formate 21-aceta te
REACTION
Δ —Δ ;3-OFo— 3-C=0 ; 21-OAc -»21 -OH
-
5 4
Δ —Δ ; 21-OAc —21 -OH; 3/3-OH—3-C=0
3 /3 -OH-3-C=0; Δ 5 - Δ 4
3/3-glycoside (saponin) —* 3/3-OH
1
Δ
1
Δ 1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
(with asparagine - no react ion)
(without a s p a r a -g i n e - d e g r a d a -tion)
utilization
Δ —Δ ; 3/3-OH— 3 - C = 0
Δ5-*Δ4; 3/3-OH-3 - C = 0 ; 21-OAc —21-OH
Δ —Δ ;3j3-OFo - 3 - C = 0 ; 21-OAc —21-OH
R E F .
P-744
P-744
M-544
A-19; A-21 ; A-22; B-50
S-795
1-430
1-430
1-430
1-430
1-430
1-430
1-430
A-19
M-595
P-744
P-744
P-744
415
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus:
FLAVOBACTERIUM FOMES
FRAMETES FUMAGO
FUSARIUM
(Basidio. - Agaricales) (Taxonomy Unclear - Probably TRAMETEÉ (Imperf. - Moniliales) (Imperf. - Moniliales)
SPECIES
species
FOMES
pinicola
robs lus
1 spec ies
FRAMETES (see TRAMETES)
1 Pi n i
FUMAGO
species
FUSARIUM
aquaeductum
(var. d imerum)
SOURCE
RIND (35-1)
RIND (38-3) (39-2)
FRI
IAM
IAM
IAM
FRI
CZAS
CZAS
SUBSTRATE
3/3,17a, 21 - tr ihydroxy -5 - p r eg -nen-20-one 3 ,21-d iace ta te
3/3,21-dihydroxy-5-pregnen-20-one
3/3,21-dihydroxy-5-pregnen-20-one 21-aceta te
3/3,17a, 21- t r ihydroxy-5-pr eg-nen-20-one
3/3,17a, 21- t r ihydroxy-5-pregnen-20-one 21-aceta te
3ß, 21-dihydroxy-16a, 17a-oxido-5-pregnen-20-one 21-aceta te
17a, 21-dihydroxy-4-pregnene -3 ,20-dione
17a, 21-dihydroxy-4-pregnene -3 ,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
4-andr os tene-3 ,17-d ione
4 -p regnene-3 ,20-d ione
4-andr os tene-3 ,17-d ione
4 -pregnene-3 ,20-d ione
REACTION
-
3/3-OH->3-C=0; Δ5->Δ4
3 /3 -OH^3-C=0:
3/3-OvH^3-C=0; Δ 5 - Δ 4
3 /3 -OH^3-C=0: Δ 5 - Δ 4
3/3-OH->3-C=0: Δ ^ Δ 4
-
-
—
—
-
6/3-ΟΗ;15α-ΟΗ
-
6/3-ΟΗ;15α-ΟΗ
R E F .
Ρ-744
Ρ-742
Ρ-742
Ρ-742
Ρ-742
Ρ-742
S-849
S-849
S-849
S-849
S-849
C-97
C-97
C-97
C-97
416
TABLE I I I
T r a n s f o r m a t i o n s by G e n u s : FUSARIUM
SPECIES
a r thoce ra s
aspidioti
avenaceum
(var. herbarum)
1 batatat is
bulbigenum
(var. plum)
buxicola
caucas icum (poss. synonym for
solani)
SOURCE
OIAß (F-75)
OIAB (F-61)
CZAS
CZAS
OIAB (F-68)
ATCC-7618
OIAß (F-59)
OIAB (F-76)
CZAS
C
SUBSTRATE
17a, 21-dihydroxy-4-pregnene -3,20-dione
17o, 21-dihydroxy-4-pregnej ie-3,20-dione
4-andros tene-3 ,17-d ione
4-pregnene-3 ,20-d ione
4 -androstene -3 ,17 -dione
4-pregnene-3 ,20-d ione
1 la, 21 -dihydr oxy -4 -pr egnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
4 -andros tene-3 ,17-d ione
4-pregnene-3 ,20-d ione
5a -andr ostane -3 ,17 -dione
3/3 - hydroxy - 5 -andr osten -17 -one
4 -androstene -3 ,17 -dione
1,4 -andr ostadiene -3 ,17 -dione
3/3-hydroxy-5a-pregnan-20-one aceta te
5a-pregnane-3 ,20-d ione
REACTION
-
oxidation -products not identified
6/3-OH;15a-OH
-
6/3-OH;15a-OH
-
oxidation -products not identified
1
Δ
oxidation -products not identified
-
6j3-OH;15a-OH
-
Δ 1 ' 4
Δ1; 3 / 3 - O H -3 - C = 0 ; Δ 5 - Δ 4
1
Δ
Δ1; 17-C = 0 -17a -oxa -17-C=0
1 7 - C = 0 - 17a-o x a - 1 7 - C = 0
A 1 . 4.
Δ ' ; 3/3-OAc->3-C=0; 17/3-OAc -> 1 7 - C = 0
17/3-Ac-+17-C=0 3 ß - O A c - 3 - C = 0
Δ 1 ' 4 ; 17/3-Ac — 1 7 - C = 0
17ß-Ac— 17-C=0
R E F .
K-462
K-462
C-97
C-97
1 C-97
C-97
K-462
C-125
K-462
K-462
C-97
C-97
V-1056
V-1056
V-1056; W-1095
W-1095
W-1095
V-1056
V-1056
V-1056
V-1056
1
TABLE I I I
417
T r a n s f o r m a t i o n s by G e n u s : FUSARIUM
SPECIES
caucasicum
(For Ref. W-1116, 1117 and 1118 -interact ion of un-sa tura ted and sa tura ted s t e ro ids . )
SOURCE
C
CBS
SUBSTRATE
3/3-hydroxy-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
21-hydroxy-4 -p regnene-3 ,20-dione
andros tane-3 ,17-d ione
3/3-hydroxy-5-androsten-17-one
17/3-hydroxy-4-androsten-3-one
4 -andr ostene -3 ,17 -dione
3/3-hydroxy-5o-pregnan-20-one
3ß-hydroxy-5a-pregnan-20-one ace ta te
5a-pregnane-3 ,20-d ione
5/3-pregnane-3, 20-dione
5a -16-pregnene-3 ,20-d ione
3/3-hydroxy-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
REACTION
1 5 4 Δ ; Δ - Δ ; 17j3-Ac->17-C=0 3/3-OH-3-C = 0
17/3-Ac — 1 7 - C - O
17ß-Ac 3-» 17-C = 0 ; Δ
Δ1; 17/3-(20-C = 0-21-OH) -» 1 7 - C = 0
Δ 1 , 4
Δ ^ β - Ο Η -» 3-C = 0 ; Δ5->Δ4
Δ ' ; 1 7 / 3 - Ο Η -> 1 7 - C = 0
1
Δ
Δ > ; 3 /3-OH^3-C=0; 17)3-Ac-»17-C=0
1
Δ ; 3ß-OAc-3 -C = 0 ; 17j3-Ac-17-C=0
A 1 ' 4 ; 17/3-Ac^l7-C=0
Λ 1 4
Δ > ; 17/3-Ac -»17a-o x a - 1 7 - C = 0
17/3-Ac — 1J-C=0; Δ
-1 4
Δ - 1 7 - A c - » 1 7 - C = 0
1 5 4 Δ ; Δ —Δ ; 17/3-A c - 1 7 - C = 0 ; 3 /3-OH^3-C=0
Δ1; 17]3-Ac—17a - o x a - 1 7 - C = 0
Δ1;17β-Αο — 1 7 - C = 0
R E F .
V-1056; W-1095
V-1056
V-1056; W-1095
V-1056; W-1095
W-1116
W-1118
W-1118
W-1116; W-1117; W-1118
W-1118
V-1056
W-1116; W-1118
W-1116
W-1116
W-1116
W-1118
W-1118
W-1116
W-1116; W-1117; W-1116;
418
TABLE I I I
Transformat ions by Genus: FUSARIUM
SPECIES
caucasicum
SOURCE
CBS
CZAS
SUBSTRATE
4-pregnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
16a, 17ö-ox ido-4-pregnene-3 ,20-dione
3/3-hydroxy-5,16-pregnadien-20-one
4 ,16-pregnad iene-3 ,20-d ione
17/3-hydroxy-4-androsten-3-one ace ta te
17/3-hydroxy-4-androsten-3-one benzoate
17/3-hydroxy-4-androsten-3-one isobutyrate
17/3-hydroxy-4-androsten-3-one formate
17/3 -hyd roxy-4 -and ros t en -3 -one propionate
4 -andr ostene -3 ,17 -dione
REACTION
17/3-Ac-1 7 - C = 0
A1;17/3-(20-C= O-21-OH) -1 7 - C = 0
Δ1; 16α, 17a-oxido-17/3-Ac— 1 7 - C = 0
1 5 4 16
Δ ; Δ —Δ ; Δ -1 7 - A c - 1 7 - C = 0 ; 3 /3-OH-3-C=0
1 16
Δ ; Δ -17-Ac ->17-C = 0
Δ1; 17j6-OAc-1 7 - C = 0
Δ ;17/3-OAc— 17a-oxa-17-C=0
-
-
Δ ;17/3-OFo-> 17a-oxa-17-c=o ^-,ΙΊβ-ΟΈΌ-* 1 7 - C = 0
A1;17i3-OPr — 17a-oxa-17-C=0
Δ1; 17j3-OPr -+ 1 7 - C = 0
6/3-OH
15a-OH 1
Δ
Δ 1 ; 1 7 - 0 = 0 - > 17/3-OH
1 7 - C = 0 - * 1 7 a -o x a - 1 7 - C = 0
R E F .
W-1116
W-1118
W-1118
W-1118
W-1118
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97; H-399
C-97
C-97
TABLE I I I
419
T r a n s f o r m a t i o n s by Genus: FUSARIUM
SPECIES
caucas icum
cocophilum
coeruieum
concolor
cu lmorum
d imerum
1 d ive r s i sporum
SOURCE
CZAS
PIRI
CZAS
OIAB (F-83)
ces CZAS
EM (2092)
VEB
OIAB (F-39)
OIAB (F-43)
SUBSTRATE
4-andros tene -3 ,17-d ione
17/3-hydroxy-4-androsten-3-one
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -andros tene -3 ,17-d ione
4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
4 -andros tene -3 ,17-d ione
4 -p regnene-3 ,20-d ione
17α, 21 -dihydroxy -4-pregnene -3,20-dione
4 -p regnene-3 ,20-d ione
17a, 21 -dihydroxy -4-pregnene -3 ,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
REACTION
A 1 ;17-C = 0 -17a-oxa-17-
c=o 1
Δ
17j3-OH — 17-C=0
17/3-OH-17a-oxa-17-C = 0
Δ ;17/3-OH — 1 7 - C = 0
Δ ;17/3-OH-+17a o x a - 1 7 - C = 0
A^HjS-Ac — 1 7 - C = 0
Δ ; 17/3-Ac -17/3-OH
17/3 -Ac— 17-C = 0
Δ ; 17/3-Ac -> 17a-oxa-17-C=0
Δ ; 17/3-Ac—17a-oxa-17-C = 0
6β-ΟΗ;15α-ΟΗ
--
15α-OH
6β-ΟΗ;15α-ΟΗ
-l i a - O H
15α-OH
6/3-OH
11α-OH
oxidation -products not identified
R E F .
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
M-588
C-97
C-97
K-462
M-599
C-97
C-97
M-557
K-452
K-462
K-462
K-462
420
TABLE I I I
T r a n s f o r m a t i o n s by G e n u s : FUSARIUM
SPECIES
equiseti
expansum
gibosum
(var. acuminatum)
gigas
g raminearum
herberum
heterosporum
javanicum
SOURCE
EM{2083)
CZAS
CZAS
CZAS
CZAS
OIAB (F-55)
CZAS
ATCC-12575
SUBSTRATE
lia, 21 -dihydroxy -4 -pregnene -3,20-dione 21-aceta te
17α, 21-d ihydroxy-1 ,4 -pregna-diene-3 ,20-dione
17a, 21-d ihydroxy-4 ,6 -pregna-d iene-3 ,20-dione
1 7 a , 2 1 - d i h y d r o x y - l , 4 , 6 - p r e g n a -t r iene -3 ,20 -dione
4 -andros tene -3 ,17-d ione
4-pregnene-3 ,20-d ione
4 -androstene -3 ,17 -dione
4 -andros tene-3 ,17-d ione
4-pregnene-3 ,20-d ione
4 -androstene -3 ,17 -dione
4-pregnene-3 ,20-d ione
4 -andros tene-3 ,17-d ione
4-pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
4 -andros tene-3 ,17-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
l l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
4-pregnene-3 ,20-d ione 20-cyclo-ethyleneketal
4 -p regnene -3 ,11 ,20 - t r i one
REACTION
l i a - O H
l i a - O H ; 21-OAc ^ 2 1 - O H
l l a - O H
l i a - O H
l l a - O H
6/3-OH; 15a-OH
—
6/3-OH; 15a-OH
-
6j3-OH; 15a-OH
-
6/3-OH; 15a-OH
—
6/3-OH; 15a-OH
-
oxidation -products not identified
6/3-OH; 15α-ΟΗ
-
17/3-Ac->17-C=0 Δ1; l l a - O H
Δ1; 17/3-Ac-» 17a-oxa-17-C=0
1
Δ ; 17/3-Ac -» 17/3-OH; l l a - O H
Δ1; 17/3-Ac — 17a-oxa-17-C=0
1
Δ
Δ1; 17/3-Ac-» 17a-oxa-17-C=0
R E F .
M-557
M-577
M-557
M-557
M-557
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
K-462
C-97
C-97
F-274
F-274
F-274
F-274
F-251
F-274
4-pregnene-3,20-dione
TABLE I I I
421
T r a n s f o r m a t i o n s by Genus : FUSARIUM
SPECIES
javanicum
la ter i t ium
SOURCE
CZAS
QM-524
CZAS
SUBSTRATE
4-andros tene -3 ,17-d ione
4 -p regnene-3 ,20-d ione
4 - p r e g n e n e - 3 , 20-dione
l l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17/3-hydroxy -4 - andros ten-3 -one aceta te
17/3-hydroxy -4 - andros ten-3 -one benzoate
17/3-hydroxy-4-androsten-3-one isobutyrate
17/3-hydroxy-4-androsten-3-one for mate
17/3-hydroxy -4 - andros ten-3 -one propionate
4 - andr osten e- 3 ,17-dione
REACTION
6/3-OH;15a-OH
Δ ;17ß-Ac-> 17a-oxa-17-C=0
A 1 ; l l a -OH;17 j3 -A c - 1 7 - C = 0
Δ ; 17/3-Ac-> 17a-oxa-17-C = 0
Δ*; 17/3-Ac-17/3-O H ; l l o - O H
Δ1; 17/3-Ac — 1 7 - C = 0
1
Δ
Δ1; 20-C = O -20/3-OH
Δ ; 17/3-OAc-17-C = 0
Δ ;17/3-OAc— 17a - o x a - 1 7 - C = 0
-
-
1
Δ ; 17ß-OFo— 17a-oxa-17-C=0
Δ ; 17/3-OFo-17-C = 0
Δ1; 17 /3 -OPr -1 7 a - o x a - 1 7 - C = 0
Δ1; 17 /3 -OPr -1 7 - C = 0
6/3-OH
15α -OH
Δ 1 ; 1 7 - C = 0 -17/3-OH
1 7 - C = 0 - 1 7 a -o x a - 1 7 - C = 0
1 7 a - o x a - 1 7 - C = 0
R E F .
C-97
C-97
F-274; F-278
F-278
F-287
F-287
F-276
F-275
F-275
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
422
TABLE I I I
T r a n s f o r m a t i o n s by Genus: FUSARIUM
SPECIES
la ter i t ium
(var. fructigenum)
lini
SOURCE
CZAS
OIAB (F-52)
OIAB ( F - l )
ATCC-9593
CBS
SUBSTRATE
17j3 -hydroxy -4 - androsten -3 -one
4 -pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydr oxy -4 -pregnene -3,20-dione
4 -p regnene-3 ,20-d ione
17/3-hydroxy-4-androsten-3-one
4 -andros tene -3 ,17-d ione
4 -p regnene-3 ,20-d ione
(6/3,15a-diOH - co r r ec t ed to 12/3,15a-diOH; Dodson, R. M. , Helv. 48; 1933, 1965)
21 -hydroxy-4 -p regnene-3 ,20-dione
14a ,21-d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3 ,20- dione 21 - ace täte
REACTION
1
Δ
17ß-OH -1 7 - C = 0
17/3-OH-»17a-o x a - 1 7 - C = 0
Δ1; 17β-ΟΗ -1 7 - C = 0
Δ ; 17/3-OH — 17a - oxa - 17 - C= 0
Δ ; 17/3-Ac — 1 7 - C = 0
Δ1; 17/3-Ac-» 17/3-OH
17/3-Ac-* 17-C=0
1
Δ ; 17/3-Ac^l7a-o x a - 1 7 - C = 0
oxidation -products not identified
oxidation -products not identified
15a-OH
15a-OH
15a-OH
15a-OH
6/3,15a-diOH
15a-OH; Δ*-» 5 | - H
15a-OH
15a-OH
15a-OH; 21-OAc — 21-OH
R E F .
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
K-462
K-462
M-599
T-980
T-980
T-980
T-980
T-980
T-980; W-1074
T-980
T-980
TABLE I I I
T ransformat ions by Genus: FUSARIUM
423
SPECIES SOURCE SUBSTRATE REACTION R E F .
uni CBS
FAHU
NARI
OIAB (F-85 )
Uß
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17/3-hydroxy-4-androsten-3-one
4 -andros tene-3 ,17-d ione
4 -pregnene-3 ,20-d ione
[ 6/3,15a-OH - co r r ec t ed to 12/3,15a-diOH - Dodson, K .M. Helv. 48; 1933 (1965)]
21 -hydroxy-4 -p regnene-3 ,20-dione
14/3-hydroxy-3-keto-5/3-20(22)-cardenolide
12/3-OH
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide
3/3,14/3-dihydroxy -5/3-20(22)-cardenolide 3-aceta te
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide -3 - (L - rhamnoside 2 1 ,3 1 ,4 1 - t r i ace ta t e )
3/3,14/3-dihydroxy-5/3-20(22)-ca rdeno l ide -3- (D-cymaros ide 4 -acetate)
Πα-ΟΗ
oxidation products not identified
15a-OH
15a-OH; 17/3-OH - 1 7 - C = 0
15a-OH
15a-OH
6/3, 15a-diOH
15a-OH; Δ 5ξ-Η
15a-OH
12/3-OH
3 - C = 0 - 3 a - O H
3 - C = 0 - 3 a - O H ; 12/3-OH
12/3-OH
12/3-OH; 3/3-OAc ->3/3-OH
2 1 - O A c - 2 i - O H ; S ' - O A c - ^ - O H ; 4 1 -OAc^4 1 -OH
4 1 -OAc-4 1 -OH
W-1074
S-849
S-849
K-462
G-319
G-319
G-319
G-319
G-319
G-319
G-319
C-320; T-978
G-320; T-978
G-320; T-978
G-320; T-978
G-320; T-978
T-978
T-978
424
TABLE I I I
T r a n s f o r m a t i o n s by Genus: FUSARIUM
SPECIES
Uni
SOURCE
UB
SUBSTRATE
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide 3-[D-glucosyi-D-g lucosy l -D-cymaros ide j
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide 3-[digitoxosyl-digitoxosyl -digitoxoside -t e t raace ta te ]
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide 3-[digitoxosyl-digitoxosyl-digitoxoside ]
3/3,14/3-dihydroxy-5/3-20(22)-
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide 3-[D-rhamnoside]
3 - O a c e t y l - 1 4 - a n h y d r o -digitoxigenin
3/3, 5/3,14/3-trihydroxy-19-oxo-20(22)-cardenolide 3/3-D-glucoside
3/3,5/3,14/3-trihydroxy-19-oxo-20(22)-cardenolide 3/3-D-glucoside t e t raace ta te
3/3,5/3,14/3-trihydroxy-19-oxo-20(22)-cardenolide 3-[D-glucosyl -D-glucosyl -D-cymaros ide heptaacetate |
3/3, 5/3,14/3-trihydroxy-19-oxo-20(22)-cardenolide 3-[D-glucosyl -D-cymaros ide t e t raace ta te ]
3β, 5/3,14/3,19-tetrahydroxy-20(22) -cardenolide
14/3,16/3-dihydroxy-3-keto-5/3-20(22)-cardenolide
REACTION
digi toxigenin-3-[D-glucosyl-D-glucosyl-D-cymaros ide |—> digi toxigenin-3-[D-cymaros ide j
digi toxosyl-digitoxosyl-digitoxoside -t e t raace ta te —» digitoxosyl-digitoxosyl-digitoxoside
—
—
-
—
3j3-D-glucoside - 3/3-OH
3/3-D-glucoside t e t raace ta te -* 3/3-OH
strophanthidin-3-[D-hepta-ace ty l -D-g luco-sy l -D-g lucosy l -D-cymaros ide] -* s t rophanthidin-3 - [D-cymaro-side]
D-glucosyl -D-c y m a r o s i d e -te t raace ta te —> D-glucosyl -D-cymaros ide
-
3-C=0-^3ff-OH
R E F .
T-978
G-320; T-978
G-320; T-978
G-320; T-978
G-320; T-978
T-978
T-978
T-978
T-978
T-978
T-978
T-977
cardenolide 3-[D-cymaroside |
TABLE I I I
425
T r a n s f o r m a t i o n s by G e n u s : FUSARIUM
SPECIES
lini
lycopers ic i
SOURCE
UB
NRRL
S
TNAES
SUBSTRATE
3/3,14/3,16/3-trihydroxy-5j3-20(22) -cardenol ide
3ß, 14/3,16/3~trihydroxy-5/3-20(22) -cardenoiide 3 -D-cymaros ide 4 1 ,16-d iace ta te
3/3,14/3,16/3-trihydroxy-5/3-20(22) -cardenoiide 3 -D-cymaros ide 4 1 ,16-d iace ta te
3/3,14j3,19-trihydroxy-5a-20(22)-cardenolide
3/3, 11α, 14/3-trihydroxy-5/3-20(22) -cardenoi ide
3 - k e t o - l l a , 14/3-dihydroxy-5/3-20(22)-cardenoiide
3,11 - diketo -1 Aß - hydr oxy - 5/3 -20(22)-cardenoiide
3-keto-14/3,19-dihydroxy-4,20 (22) -cardadienol ide
3/3,14/3-dihydroxy-5/3 -16,20(22) -cardadienolide
14ß-hydroxy-3-keto-5/3-20,22-bufadienolide
3/3,14/3-dihydroxy-5/3-20, 22-bufadienolide
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
4 -p regnene-3 ,20-d ione
1 l a -hyd roxy -4 -p regnene -3 ,20 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17o, 21 -dihydroxy -4 -pregnene -3 ,20-dione
11/3,21 -dihydroxy -4 -pregnene -3 ,20-dione
1 7a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
REACTION
12/3-OH
41-OAc—4X-OH
4 1 - O A C - 4 1 - O H ; 1 6 - O A C - » 16-OH
-
-
-
-
-
-
12/3-OH
12/3-OH
-
-
-
15a-OH
6/3-OH
15a-OH
6ß-OH
X-OH; 15a-OH
—
R E F .
T-977
T-978
T-978
T-978
T-978
T-978
T-978
T-978
T-978
T-979
T-979
M-587
M-587
M-587
S-849; S-858; S-859
S-849; S-858
S-849; S-858
S-849; S-858
S-849; S-858
S-849
426
TABLE I I I
T r a n s f o r m a t i o n s by Genus: FUSARIUM
SPECIES
lycopers ic i
m a c r o c e r a s
mer i smoides
mic roc rea
moniliforme (imperfect s tage of Gibberelia fujikuroi)
(var. lactis)
(var. subglutinans)
(var. majus)
nivale
niveum
niveus
SOURCE
VEB
CZAS
CZAS
CZAS
ATCC-10052
CZAS
OIAB (F-7)
(F-5)
SY
CZAS
OIAB
S
SUBSTRATE
4-pregnene-3 ,20-d ione
4 -andros tene-3 ,17-d ione
4-pregnene-3 ,20-d ione
4 -andros tene -3 ,17 -dione
4-pregnene-3 ,20-d ione
4 -androstene -3 ,17-dione
4-pregnene-3 ,20-d ione
1 I ß , 21 -dihydroxy -4 -pregnene -3,20-dione
4-andros tene-3 ,17-d ione
4-pregnene-3 ,20-d ione
4 -androstene -3 ,17 -dione
4 -pregnene-3 ,20-d ione
4 -andros tene-3 ,17-d ione
4-pregnene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17o, 21 -dihydroxy -4 -pregnene -3,20-dione
l ,3 ,5 (10) -es t ra t r i ene-3 ,17 j3-d io l
l , 3 ,5 (10) -es t ra t r i ene-3 ,17 /3 -d io l 3-methylether
l , 3 , 5 ( 1 0 ) - e s t r a t r i e n - 3 - o l - 1 7 - o n e
4 -androstene -3 ,17 -dione
4-pregnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
4 -pregnene-3 ,20-d ione
1 l a -hyd roxy-4 -p regnene -3 ,20 -dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
REACTION
15a-OH
6j3-OH;15a-OH
-
6/3-OH;15a-OH
-
6/3-OH; 15a-OH
-
15a-OH
6/3-OH; 15a-OH
-
Öß-OH;15a-OH
-
6/3-OH; 15a-OH
-
oxidation -products not identified
oxidation -products not identified
15a-OH
6ß-OH
15a-OH
6/3-OH; 15a-OH
oxidation -produc ts not identified
-
—
11a-OH
R E F .
K-452
C-97
C-97
C-97
C-97
C-97
C-97
M-599
C-97
C-97
C-97
C-97
C-97
C-97
K-462
K-462
C-139
C-139
C-139
C-97
C-97
K-462
S-859
S-859
S-859
TABLE I I I
427
T r a n s f o r m a t i o n s by Genus : FUSARIUM
SPECIES
niveus
o r thoceras
oxysporum
(var. o r thoceras )
1 (var. aurant iacum)
poae
pruni
redolens
ro seum
SOURCE
TNAES
ATCC-10082
CBS
ATCC-7601
ATCC-9991
CZAS
FRI
OIAB (F-3)
OIAB (F-4)
OIAB (F-40)
OIAB (F-69)
EM(2087)
VEB
SUBSTRATE
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17/3-hydroxy-4-estren-3-one
17j3-hydroxy-4-estren-3-one
17a,21 -dihydr oxy -4 -pregnene -S j l l ^ O - t r i o n e
4 -andros tene -3 ,17-d ione
21 -hydroxy - 5/3 -pr egnane - 3 , 2 0 -dione aceta te
6/3-hydroxy-4-pregnene-3,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
17a, 21 -d ihydroxy-4-pregnene-3 ,11 ,20- t r ione 21-aceta te
4 -andros tene-3 ,17-d ione
4-pregnene-3 ,20-d ione
4 -androstene -3 ,17 -dione
4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
1 la, 21 -dihydroxy -4 -pr egnene -3,20-dione
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
17a, 21 -dihydroxy-4-pregnene -3 ,20-dione
17/3-hydroxy-4-androsten-3-one
4 -pregnene-3 ,20-d ione
REACTION
6/3-OH
15a-OH
15a-OH
15a-OH; 17/3-OH - 1 7 - C = 0
1
Δ
15a-OH
15a-OH;21-OAc - 2 1 - O H
15a-OH
15a-OH
15a-OH;21-OAc - 2 1 - O H
6/3-OH;15a-OH
-
6/3-OH; 15a-OH
-
-
-
-
oxidation -products not identified
oxidation -products not identified
11a-OH
6/3-OH
15a-OH
6/3,15a-diOH
R E F .
S-849
M-599
D-151
D-151
C-125
M-599
M-599
M-599
M-599
M-599
C-97
C-97
C-97
C-97
S-849
K-462
K-462
K-462
K-462
M-557
R-747
R-747
R-747
428
TABLE I I I
T r a n s f o r m a t i o n s by Genus: FUSARIUM
SPECIES
roseum
sambucinum
sa rcochroum
semi tec tum
solani
SOURCE
VEB
CZAS
CZAS
CZAS
OIAß (F-42)
AMCY
ATCC-12823
AY
C
SUBSTRATE
1 7a, 21 -dihydroxy -4 -pr egnene -3,20-dione
4 -andros tene-3 ,17-d ione
4-pregnene-3 ,20-d ione
4 -andr ostene -3 ,17 -dione
4-pregnene-3 ,20-d ione
4-andr os tene-3 ,17-d ione
4-pregnene-3 ,20-d ione
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
3/3-hydroxy-16a, 17a-oxido-5-pregnen-20-one
2a-f luoro-17a, 21 -dihydroxy - 4 -pregnene - 3 , 1 1 , 2 0 - t r ione
4 -pregnene-3 ,20-d ionê (use of spores)
1 7 G , 21 -dihydroxy -4 -pregnene -3,20-dione (use of spores)
l i a , 17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione (use of spores)
5a-andros tane-3 ,17-d ione
4 -andros tene-3 ,17-d ione
3ß -hydr oxy - 5 -andr osten -17 -one
l , 4 - and ros t ad i ene -3 ,17 -d ione
3/3-hydroxy-5a-pregnan-20-one aceta te
5α-pregnan-3 ,20-dione
REACTION
6/3-OH
15a-OH
6/3-OH; 15a-OH
-
6/3-OH; 15a-OH
-
6/3-OH; 15a-OH
-
oxidation -products not identified
11α-ΟΗ
1
Δ
1
Δ
Δ1
1
Δ
Δ 1 ' 4
1
Δ
Δ5—Δ4;3β-ΟΗ-> 3 - C = 0 ; Δ 1
-1 4
Δ 1 ' ; 3ß-OAc-*3-C = 0 ; 17/3-Ac-*17-C=0
17/3-Ac-17-C=0; 3ß-OAc-^3-C=0
17/3-Ac-»17-C=0
17/3-Ac-17-C=0
R E F .
R-747
R-747
C-97
C-97
C-97
C-97
C-97
C-97
K-462
P-746
H-401
S-835
S-835; V-1048
S-835; V-1048
V-1056·, 'vV-1095
V-1056; W-1095
V-1056
V-1056
V-1056; W-1095
V-1056
V-1056; W-1095
V-1056; W-1095
TABLE I I I
429
T r a n s f o r m a t i o n s by Genus: FUSARIUM
SPECIES
solani
*
SOURCE
C
CZAS
SUBSTRATE
3ß-hydroxy-5-pregnen-20-one
4 -p regnene-3 ,20-d ione
17α,21 -dihydroxy -4 -pr egnene -3,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21-dihydroxy-4-pregnene -3 ,11 ,20 - t r i one
l l /3 -hydroxy-3 ,20-d ike to -4-pregnen-18-o ic acid (18—*11) lactone
l l / 3 - h y d r o x y - 3 , 2 0 - d i k e t o - l , 4 -pregnadien-18-o ic acid (18 -* 11) lactone
1 Ίβ -hydroxy -4 -andros ten - 3 -one aceta te
17/3-hydr oxy-4-andros ten-3 -one benzoate
17/3-hydroxy-4 -androsten -3 -one isobutyrate
17/3-hydroxy-4-androsten-3-one formate
17/3-hydroxy-4-androsten-3-one propionate
REACTION
17/3-Ac->17-C=0
1 5 4
Δ ; Δ —Δ ;17/3-A c ^ l 7 - C = 0 ; 3 /3 -OH-3-C=0
1 7 - C = 0
(weitere Substanz)
1
Δ
A i ;17ß- (20-C = 0-21-OH) — 17-C = 0
(weitere Substanz)
1
Δ
17/3-Ac-*17-C=0
17/3-Ac-*17-C=0; 13/3-COOH -» 13/3-H; Δ1
17j8-Ac-17-C=0; 13/3-COOH -» 13α-Η; Δ1
Δ1; 17/3-Ac — 17ß-OH
17/3-Ac - x 1 7 - C = 0 ; Δ
17ß-Ac^l7/3-OH
Δ ; 17/3-OAc -» 1 7 - C = 0
ΔΧ;17β-ΟΑο — 17a-oxa-17-C=0
-
-
Δ ; 17/3-OFo— l i a - o x a - 1 7 - C = 0
Δ1;17β-ΟΡΓ-> 1 7 - C = 0
R E F .
V-1056; W-1095
V-1056; W-1095
V-1056; W-1095
V-1056
V-1053
V-1056; W-1095
V-1056
V-1053
U-1044
U-1044
U-1044
U-1044
U-1044
U-1044
C-97
C-97
C-97
C-97
C-97
C-97
A i ;17ß- (20-C
430
TABLE I I I
T r a n s f o r m a t i o n s by G e n u s : FUSARIUM
SPECIES
solani
(var. aduncisporum)
(var. argi laceum)
(var. coeruleum)
(var„ redolens)
SOURCE
CZAS
IFO
SUBSTRATE
17/3-hydroxy-4-androsten-3-one propionate
4 -androstene -3 ,17 -dione
17/3-hydroxy-4-androsten-3-one
4 -pregnene-3 ,20-d ione
4 -androstene -3 ,17 -dione
4 -pregnene-3 ,20-d ione
4 -andros tene -3 ,17-d ione
4 -pregnene-3 ,20-d ione
4 -andros tene -3 ,17-d ione
4 -pregnene-3 ,20-d ione
4 -andros tene -3 ,17-d ione
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
REACTION
Δ1; 17 /3-OPr-17a-oxa-17-C=0
6/3-OH
15a-OH
A 1 ;17-C = 0 -17/3-OH
1 7 - C = 0 — 1 7 a -oxa-17-C = 0
A 1 ; 1 7 - C = 0 - 1 7 a -oxa-17-C = 0
1
Δ
17/3-OH-17-C=0
17/3-OH-17a-o x a - 1 7 - C = 0
Δ1; 17/3-OH-1 7 - C = 0
A1;17/3-OH->17a-o x a - 1 7 - C = 0
A1;17/3-Ac -1 7 - C = 0
A1;17/3-Ac-> 17/3-OH
17/3-Ac-17-C=0 1
Δ ; 17/3-Ac— 17a-o x a - 1 7 - C = 0
6/3-OH;15a-OH
-
6/3-OH;15a-OH
-
6ß-OH;15o-OH
-
6/3-ΟΗ;15α-ΟΗ
-1
Δ
AX;17ß-Ac — 17/3-OH
R E F .
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
C-97
N-663; N-664
N-663; N-664
TABLE I I I
431
T r a n s f o r m a t i o n s by G e n u s : FUSARIUM
SPECIES
solani
(var. eumart i i )
species
SOURCE
IFO
(K-101)
(K-102)
OR
uc
VEB
EM (2070)
EM (2083)
SUBSTRATE
4-pregnene-3 ,20-d ione
3/3,21-dihydroxy-5-pregnen-20-one 21-aceta te
4 -p regnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3 ,11 ,20 - t r ione
17a ,21-d ihydroxy-4-pregnene-3, 20-dione
4 -p regnene-3 ,20-d ione
17a ,20/3 ,21- t r ihydroxy-4-preg-nene-3 ,11-d ione
1 7a, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r ione
17a -hydroxy-4 -p regnene-3 ,20-dione aceta te
3 -ketobisnor -4 - cholen -22 -al
4 -p regnene-3 ,20-d ione
17a, 21 -dihydroxy-4 -pregnene -3 ,20-dione
17a-hydroxy-16-méthylène-4-pregnene-3 ,20-d ione
17a, 21 -d ihydroxy-16-méthylène-4-pregnene-3 ,20-d ione
REACTION
Δ1; 17/3-Ac -> 1 7 - C = 0
Δ ; 17/3-Ac->17a-o x a - 1 7 - C = 0
5 4 1
Δ ->Δ ; Δ ; 3/3-O H - 3 - C = 0 ; 17/3-(20-C=O-21-OAc)->17a-oxa-17-C = 0
Δ1; 17/3-Ac-17a-o x a - 1 7 - C = 0
Δ1; 17/3-(20-C=O -21-OH) - 17a-o x a - 1 7 - C = 0
1.
Δ
-
1
Δ
1
Δ
Δ ;17 /3 -Ac^ l7a -o x a - 1 7 - C = 0
17 /3 -Ac-17-C=0
Δ ; 17/3-Ac -> 1 7 - C = 0
1
Δ
20-C=O—20/3-OH
1
Δ
15a-OH
15a-OH
11a-OH
11a-OH
11a-OH
R E F .
N-663; N-664
N-663; N-664
K-462
K-462
K-462
K-462
K-462
K-462
K-462
S-949
S-949
S-949
S-949
S-949
B-36
M-599
K-452
M-557
B-68
M-558
432
T r a n s f o r m a t i o n s by Genus:
TABLE I I I
FUSARIUM FUSICLADIUM
TAXONOMY
(Imperf. - Moniliales)
SPECIES
species
sphaer iae
sporot r ichel la
(var. poae)
sporotr ichioides
sulphureum
udum
vasinfectum
FUSICLADUM
diospir i
SOURCE
NRRL
OIAB ( F - 8 , 3 2 , 3 4 )
OIAB (36)
OR
Takeda
CZAS
CZAS
OIAB (F-41)
ATCC-7642
ATCC-10084
ATCC-7808
TNAES (B- l )
SUBSTRATE
Saponins (sapogenin glycosides)
17a, 21 -dihydroxy -4-pregnene -3,20-dione
17û!, 21 -dihydroxy -4 -pr egnene -3,20-dione
17a,21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r ione
(virtually anaerobic)
17a,20/3 ,21- t r ihydroxy-4-pr egnene -3 ,11 -dione
17a,21 -d ihydroxy-1 ,4 -pregna-diene -3 ,11 ,20 - t r i one
3/3,14/3,16/3-trihydroxy-5j3-20(22)-cardenolide
4 -andros tene-3 ,17-d ione
4-pregnene-3 ,20-d ione
4 -andros tene-3 ,17-d ione
4 -pregnene-3 ,20-d ione
4 -androstene -3 ,17-dione
4-pregnene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
5a-pregnane-3 ,20-d ione
17/3-hydroxy-4-androsten-3-one
5/3-pregnane -3 ,11 ,20 - t r i one
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
REACTION
hydrolysis of glycosides to aglycones (sapogenins)
oxidation -products not identified
-
2 0 - C = O -20/3-OH
A 1 ; 2 0 - C = O -20/3-OH
1
Δ
20-C=O -20/3-OH
3/3-OH-^3-C=0
12/3-OH
6/3-OH; 15a-OH
-
6/3-OH; 15a-OH
-
6/3-OH; 15a-OH
-
oxidation -products not identified
15a-OH
15a-OH
15a-OH
R E F .
K-478
K-462
K-462
S-951
S-951
S-951
S-951
K-434
K-434
C-97
C-97
C-97
C-97
C-97
C-97
K-462
M-599
M-599
M-599
S-849
433
T r a n s f o r m a t i o n s by Genus:
TABLE I I I FUSIDIUM
GANODERMA GELASINOSPORA
GEOTRICHUM GIBBERELLA
TAXONOMY
(Imperf. - Moniliales) (Basidio. - Agaricales) (Asco. - Sphaeriales) (Imperf. - Moniliales) (Asco. - Hypocreales)
SPECIES
species
GANODERMA
applam (applanatum)
GELASINOSPORA
t e t r a s p o r a
GEOTRICHUM
lact is
GIBBERELLA
baccata
1 cyanea
1 fujikuroi
SOURCE
Sear le (M-61-1)
FRI
ATCC-14512
FRI
C
CBS
CBS
CBS
FAKU
IFO
Takeda
SUBSTRATE
3/3-hydr oxy - 5-andr osten -17-one
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17û-(21-carboxyethyl)-17/3-hydroxy-4-andros ten-3-one gamma lactone
17a, 21 -dihydroxy -4-pregnene -3 ,20-dione
4 -andros tene -3 ,17-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
d, 1-21-hydroxy-4-pregnene-3,20-dione
24-ethyl-5 ,22-choles tadien-3/3-ol
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide
3/3,14/3,16/3-trihydroxy-5/3-20(22)-cardenol ide
REACTION
7a-OH
1 7 - C = 0 -17/3-OH
l i a - O H
7a-OH
-
15a-OH
15a-OH
15a-OH
15-OH
d, l->d-15a-OH + 1
15-OH
15a-OH
-
12/3-OH
3/3-OH-3-C = 0
3/3-OH^3-C = 0 ; 16/3-OH -1 6 - C = 0
R E F .
D-175
D-175
S-849
T-1035
S-849
U-1043
M-585; U-1043
U-1043
M-599
W-1102
M-599
M-599
S-849
N-651
K-434
K-434
434
TABLE I I I
T r a n s f o r m a t i o n s by G e n u s : GIBBERELLA
SPECIES SOURCE SUBSTRATE REACTION R E F .
saubinetti
CBS
FRI
TBRI
17/3 - hydr oxy -1 la - methy 1 -4 -andros ten-3-one
4 -androstene -3 ,17 -dione
11/3-hydroxy-4-androstene -3,17-dione
21-hydroxy-4 -p regnene-3 ,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
4,9(11) -pregnadiene-3 ,20-d ione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
4-pregnene-3 ,20-d ione
17a-hydroxy-4-pregnene-3 ,20-dione
21-hydroxy-4-p regnene-3 ,20-dione
11/3,21 -d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
14ß-hydroxy-3-keto-5/3-20(22)-cardenolide
3/3,14/3-dihydroxy -5/3-20(22)-cardenolide
6j3-OH
6ß-OH
15α-OH
6/3-ΟΗ
15α-OH
l l - O O (via l lß -OH) 6/3 -OH
15α-OH
6/3-OH
15α-ΟΗ
15α-ΟΗ
6/3-OH; l i a - O H
15a-OH
X-OH; 15a-
15a-OH
6β-ΟΗ
15a-OH
12/3-OH
3 - C = 0 ^ 3 a
3-C=0->3a-12/3-OH
12/3 -OH
OH
OH
OH:
U-1043
U-1043
U-1043
U-1043
U-1043
U-1043
U-1043
U-1043
U-1043
U-1043
M-599
S-849
S-849; S-858; S-859
S-849; S-858
S-859
S-849; S-858
S-858
S-849
S-849; S-858
S-858
S-859
0-699
0 -699
0-699
0 -699
C
S 15α-OH
6β-ΟΗ
TABLE I I I
TAXONOMY
435
Transformat ions by Genus: GIBBERELLA GLIOCLADIUM (Imperf. - Moniliales)
SPECIES
saubinett i
zeae
GLIOCLADIUM
catenulatum
SOURCE
TBRI
ATCC-10910
ATCC-10523
SUBSTRATE
3/3,14/3,16/3-trihydroxy-5/3-20(22)-cardenolide
3/3,14/3, 16ß-trihydroxy-5/3-20(22)-cardenolide 16 -aceta te
l l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
5a -p regnane -3 ,11 ,20 - t r i one
5/3-pregnane-3,20-dione
5 /3-pregnane-3 ,6 ,20- t r ione
3/3-hydroxy-21-ethyl-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione 20-cyc io-ethyleneketal
6ß -hydroxy-4 -p regnene -3 ,20 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
2 1 - m e t h y l - 4 - p r e g n e n e - 3 , 2 0 -dione
17a, 21 -dihy d roxy-4 -p regnene -3,20-dione
REACTION
12/3-OH
12/3-OH
16/3-OAc — 16/3-OH
12/3-OH; 16/3-OAc — 16/3-OH
15a-OH
15a-OH
17/3-Ac^l7-C=0
17/3-Ac—17-C=0
17/3-Ac^l7-C=0
17j3-Bu—17-C = 0
17/3-Ac— 17-C=0
17/3-Ac -> 17-C = 0 ;6ß -OH
6/3-OH
17/3-Ac^l7-C=0
17/3-(20-C=O-21-OH) -> 1 7 - C = 0
17/3-(20-C=O-2 1 - O H ) -1 7 - C = 0 ; 6/3-OH
17/3-Pr-*17-C=0
17a-OH-17/3-(20-C=O-21-OH) —17-C=0
17a-OH-17/3-(20-C=O-21-OH) — 17-C = 0;6/3-OH
R E F .
Q-699
0-699
0-699
Q-699
M-599
M-599
M-633
M-633
M-633
M-633
M-633; P-726
M-633; P-726
F-251
M-633
M-633
M-633
M-633
M-633
M-633
436
TABLE I I I
Transformat ions by Genus: GL IOCLADIUM
SPECIES
catenulatum
del iquescens
luteolum
roseum
SOURCE
ATCC-10523
NRRL
CBS
CBS
ATCC-10521
FRI
S
SUBSTRATE
l i a , 17a, 21 - tr ihydroxy - 4 - p r e g -nene -3 ,20-d ione
4 -pr egnene - 3 , 1 1 , 2 0 - t r ione
17a, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r ione
17a, 21-dihydroxy-4-pregnene -3 ,11 ,20- t r ione 21-aceta te
3 -ketobisnor -4 -cholen-22 -al
Diosgenin
4 -dehydrotigogenone
21-hydroxy-4-p regnene-3 ,20-dione aceta te
21 -hydroxy-4 -p regnene-3 ,20-dione aceta te
3 /3 ,17a ,20a- t r ihydroxy-5a-pregnane
21-hydroxy-4 -p regnene-3 ,20-dione aceta te
17α, 21-dihydroxy-4-pregnene -3,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
1 I ß , 21 -dihydroxy -4-pregnene -3,20-dione
REACTION
17α-ΟΗ-17β-(20-C=0-21-OH) — 17-C = 0
17 j3 -Ac^ l7 -C=0
17a-OH-17/3-(20-C=0-21-OH) -1 7 - C = 0
17a-OH-17/3-(20-C = 0 - 2 1 - O A c H 1 7 - C = 0
20a-HC=O — 20/3-HC=O
2 2 - C = 0 - 2 2 - O H
-
~
-
17/3-(20-C=O-21-O A c H 1 7 - C = 0
17/3-(20-C=O-2 1 - O A c H 1 7 - C = 0 ; 6/3-OH
17/3-(20-C=O-21-OAc)->17-C=0
17/3-(20-C=O-21-OAc)->17-C=0; 60-OH
11α-ΟΉ-1Ίβ-(20α -OH-21-H) -> 1 7 - C = 0
17/3-(20-C=O-21-O A c H l 7 - C = 0
17/3-(20-C=O-21-OAc)-»17-C=0; 6/3-OH
-
1
Δ
1
Δ
R E F .
M-633; M-637
M-633
M-633
M-633
W-1068
W-1068
M-587
M-587
M-587
M-633
M-633
M-633
M-633
M-633
M-633
M-633
S-859
S-857; S-859
S-857; S-859
Sarsasapogenin
437
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by G e n u s : GLIOCLADIUM GLOEOSPORIUM (Imperf0 - Moniliales)
SPECIES SOURCE SUBSTRATE REACTION
species
GLOEOSPORIUM
cyclaminis
foliicolum
kaki
laeticola
NG
NRRL
OR
KAG
FAKU (438)
KAG
TNAES
1 7a, 21 -dihydroxy -4 -pregnene -3,20-dione
11/3,17a, 21 - tr ihydroxy -4 -p reg -nene -3 ,20-dione
17a, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r ione
5-cholesten-3/3-ol (sole carbon source)
24/3-methyl -5 ,7 ,22-choles ta -trien-3j3-ol (sole carbon source)
plant saponins
3j3-(N, N-dimethylamino) -5 -conenine
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
|4 -pregnene -3 ,20 -dione
17a -hydroxy-4 -p regnene -3 ,20 -dione
|21-hydroxy-4-pregnene-3 , 20-dione
11/3,21 -dihydroxy -4 -pregnene -3 ,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy-4 -pregnene -3,20-dione
|l 7a, 21-d ihydroxy-4-pregnene-3,20-dione
uti l ization
util ization
3/3-N-(CH3)2-> 3-C = 0 ; Δ5->Δ4
6/3-OH
l l a - O H
11a-OH
6 ß , l l a - d i O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
s roseum
R E F .
S-857; S-859
S-857; S-859
S-857; S-859
S-793c
S-793c
K-478
D-148
K-464
K-464
S-849
K-464
S-849; S-855
S-849; S-855
S-849; S-855
S-849; S-855
S-849; S-855
S-849; S-855; S-859
S-849
S-849
S
S
1
Δ
1
Δ
438
TABLE I I I
T r a n s f o r m a t i o n s by Genus: GLOEOSPORIUM GLOMERELLA
TAXONOMY
(Asco. - Sphaeriales)
SPECIES
laeticola
ol ivarum (taxonomically -perfect s tage of Glomerel la cingulata)
GLOMERELLA
cingulata
*
1 *
SOURCE
TNAES
KAG
NI
TNAES
ATCC-10529
ATCC-10530
ATCC-10531
ATCC-10532
ATCC-10533
ATCC-10534
SUBSTRATE
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4-pregnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene-3,20-dione
l l / 3 ,17a ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3 ,11 ,20- t r ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-16a-methyl-5a-pregnane-3 ,20-d ione
17a, 21-d ihydroxy-1 ,4 -p regna-d iene-3 ,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
16/3-ethyl-17a,21-dihydroxy-l , 4 -pregnadiene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-16a-me thy 1-1 ,4-pregnadiene-3 ,20-dione
16a- te r t -bu ty l -17a , 21 -dihydroxy -5a-pregnane-3 ,20-d ione
16ß-ethyl-17a, 21-dihydroxy -5a-pregnane-3 ,20-d ione
REACTION
l l a - O H
1
Δ
2 0 - C = O -20/3-OH
Δ 1
Δ
1
Δ
1
Δ
20-C = O-> 20/3-OH
Δ1; 20-C=O -20/3-OH
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
R E F .
S-849
K-464
K-464
K-465
K-465
K-465
K-465
K-465
K-465
S-859
C-109
C-109
C-109
C-109
C-109
C-109
C-109
C-109
C-109
TABLE I I I
439
T r a n s f o r m a t i o n s by G e n u s : GLOMERELLA
SPECIES SOURCE SUBSTRATE REACTION R E F .
cingulata ATCC-10534
fluctigena
ATCC-12097
FRI
KAG
QM-1407
TNAES
1 la, 21 -dihydr oxy -16a - methy 1 -5a -pregnane-3 ,20-d ione
17a,21-dihydroxy-16/3-methyl-5a -pregnane-3 ,20-d ione
17α, 21-dihydroxy-4-pregnene -3 ,20-dione
1 la, 21 -dihydroxy -16a - methy 1 -4 -p regnene-3 ,20-d ione
1 la, 21 - dihydr oxy -16/3 - methy 1 -4 -pregnene-3 ,20-d ione
17a,21-dihydroxy-16/3-methyl-4 -pregnene-3 ,20-d ione 2 1 -aceta te
D -nor -1 ,4 -pregnadiene - 3 , 2 0 -dione
1 la, 21 -dihydroxy - 1 , 4 -pr egnadiene-3 ,20-dione
17a, 21-dihydr o x y - 1 , 4 -pregnadiene-3 ,20-d ione 2 1 -aceta te
16j3-ethyl- 17a, 21 -dihydroxy -1,4 -pregnadiene -3 ,20-d ione
17a, 21-dihydroxy-16a-methyl -1,4 -pregnadiene -3 ,20 -dione
17a, 21 -dihydr oxy-16/3- methy 1-1 ,4-pregnadiene -3 ,20-d ione
| 3 - h y d r o x y - l , 3 , 5 ( 1 0 ) - e s t r a t r i e n -17-one
17a, 21-dihydroxy-4-pr egnene-3,20-dione
17a, 21-dihydroxy-4-pr egnene -3 ,20-dione
17a, 21 -dihydr oxy-16/3-methyl -4-pregnene -3 ,20-dione 2 1 -ace ta te
17a ,21-d ihydroxy-4-pregnene-3,20-dione
11a-OH
11a-OH
l l a - O H
l l a - O H
l l a - O H
l l a - O H ; 21-OAc-> 21-OH
l l a - O H
l l a - O H
l l a - O H ; 2 1 - O A c ^ 21-OH
l l a - O H
l l a - O H
l l a - O H
7a-OH
15a-OH
l l a - O H
6/3-OH
l l a - O H
l l a - O H ; 2 1 - O A c -21-OH
l l a - O H
C-109
C-109
C-109
C-109
C-109
C-109
R-763
C-109
C-109
C-109
C-109
C-109
L-494
L-494
S-849
K-464
K-464
C-109
S-849
440
TABLE I I I
T r a n s f o r m a t i o n s by Genus: GLOMERELLA
SPECIES
fusaroides
*
*
glycines
SOURCE
ATCC-9552
ATCC-3422
SUBSTRATE
l ,3 ,5 (10) -es t ra t r i en -3 ,17 /3 -d io l
3 - h y d r o x y - l , 3 , 5 ( 1 0 ) - e s t r a t r i e n -17-one
17a ,21-dihydroxy-16ß-methyl -5a-pregnane-3 ,20-d ione
17α, 21 -dihydroxy-4-pregnene -3,20-dione
l ,3 ,5 (10) -es t ra t r i ene-3 ,17 j3 -d io l
3-hydroxy - 1 , 3 , 5 ( 1 0 ) - e s t r a t r ien-17-one
REACTION
7a-OH
15a-OH
7a-OH; 17/3-OH -» 1 7 - C = 0
15a-OH; 17j3-OH — 1 7 - C = 0
7a-OH
15a-OH
7a-OH; 1 7 - C = 0 -17/3 -OH
15a-OH; 1 7 - C = 0 -Πβ-ΟΕ
l l a - O H
l i a - O H
7a-OH
15a-OH
7a-OH; 1 7 / 3 - O H -1 7 - C = 0
7a-OH
15a-OH
7a-OH; 1 7 - C = 0 - + 17β-ΟΗ
15a-OH; 1 7 - C = 0 — 17β-ΟΗ
R E F .
L-495; L-497
L-495; L-497
L-497
L-497
L-494; L-495; L-497
L-494; L-495; L-497
L-497
L-494; L-497
C-109
C-109
L-495; L-497
L-495; L-497
L-497
L-495; L-497
L-495; L-497
L-497
L-497
TABLE I I I
441
T r a n s f o r m a t i o n s by G e n u s : GLOMERELLA
SPECIES
glycines
gosypii (gossypii)
lagenar ium *
1 *
major *
1 *
I mume *
SOURCE
ATCC-11871
CBS
IAM
CBS
S
TNAES
CBS
KAG
SUBSTRATE
3-hydroxy- l , 3 ,5 (10 ) -e s t r a t r i en -17-one
16a- t e r t -butyl -17a, 21-dihydroxy -5a-pregnane-3 ,20-d ione
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
16/3-ethyl-17a, 21 -dihydroxy -5a-pregnane-3 ,20-d ione
17a, 21-dihydroxy-4-pr egnene -3,20-dione
1 7 a , 2 1 - d i h y d r o x y - l , 4 -pregnad iene- 3 ,20-dione
17a, 21-d ihydroxy-1 ,4 -pregnadiene-3 ,20-d ione 2 1 -aceta te
16a - ter t - butyl -17a ,21 -dihydroxy -1,4 -pregnadiene -3 ,20-dione
4 -pregnene-3 ,20-d ione
17a-hydroxy-4-pregnene-3,20-dione
21-hydroxy-4-pr egnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21-dihydroxy-16/3-methyl -1 ,4-pregnadiene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
REACTION
7a-OH
15a-OH
15a-OH; 1 7 - C = 0 ^ 17/3-OH
11a-OH
—
l l a - O H
11a-OH
l l a - O H
l l a - O H ; 2 1 - O A c -21-OH
l l a - O H
l l a - O H
6/3, l la-diOH
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
R E F .
L-494
L-494
L-494
C-109
S-849
C-109
C-109
C-109
C-109
C-109
S-849; S-855
S-849; S-855
S-849; S-855
S-849; S-855
S-849; S-855
S-849
C-109
C-109
K-464
442
TABLE I I I
T r a n s f o r m a t i o n s by Genus: GIOMERELLA GNOMONIA
TAXONOMY
(Asco. - Sphaeriales)
SPECIES
phacidiomorpha *
rubicola *
GNOMONIA
cingulata
e r rabunda
e ry thros toma
fimicola
f ragar iae
SOURCE
CBS
CBS
SQ
SQ
SQ
SQ
ATCC-11430
SUBSTRATE
17a, 21-dihydroxy-4-pregnene -ίΓ, 20-dione
16a - t e r t -bu ty l -17a ,21-dihydroxy -1 ,4 -pr egnadiene -3,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
17a, 21-dihydroxy-16a-methyl -4-pr e gnene - 3,2 0 - dione
4 -pregnene-3 ,20-d ione
17a, 21-dihydroxy-16a-methyl -4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
17a, 21-dihydroxy-16a-methyl -4-pregnene -3,20-dione
4-pregnene-3 ,20-d ione
17a, 21-dihydroxy-16-methyl -4 -pregnene-3 ,20-d ione
17/3 - hy dr oxy - A - nor - 3 -andros ten-2-one
17/3-hydroxy-4-androsten-3-one
17/3-hydroxy-17a-methyl-4-andros ten-3-one
17a -oxa -D-homo-4-andros t ene -3,17-dione
4-pregnene-3 ,20-d ione
16a-hydroxy-4-pregnene-3,20-dione
21-hydroxy-4-pregnene-3,20-dione
9a- f luoro- l l j3-hydroxy-4-pregnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
REACTION
l i a - O H
l i a - O H
l l a - O H
2/3-OH
2/3-OH
2/3-OH
2/3-OH
2/3-OH
2/3-OH
2/3-OH
2ß-OH
1/3-OH
2/3-OH
2/3-OH
2/3-OH
2/3-OH; 16a-OH
2/3-OH
2/3-OH
2/3-OH
2/3-OH
R E F .
C-109
C-109
C-109
L-496
L-496
L-496
L-496
L-496
L-496
L-496
L-496
L-496
L-496
L-496
L-496
L-499
L-496; L-499
L-496
L-496
L-496
443
TABLE I I I
T r a n s f o r m a t i o n s by G e n u s : GNOMONIA GRAPHIOLA GUIGNARDIA GYMNOPILUS HANSENULA
TAXONOMY
(ßasidiOo - Ustilaginales) (Asco. - Sphaeriales) (Basidio. - Agaricales) iAsco. - Endomvcetales)
SPECIES
f ragar iae
GRAPHIOLA
cyl indrica
GUIGNARDIA
1 camel l iae
GYMNOPILUS
junenius
1 spec ies
HANSENULA
1 anomala
SOURCE
ATCC-11430
NI
FRI
AL (C-142)
AL (2-6-69)
NRRL
SUBSTRATE
6a-f luoro-17a, 21-dihydroxy 4 -pregnene-3 ,20-d ione
21-hydroxy-16a ,17a-oxido-4-pregnene-3 ,20-d ione
17a, 21-dihydroxy-16a-methyl -4 -pregnene-3 ,20-d ione
6 a - f l u o r o - 1 6 a , 1 7 a , 2 1 -t r i hydroxy-4 -p regnene -3 ,20 -dione 16,17-acetonide
4 -p regnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
l l j 3 ,17a ,21- t r ihydroxy-4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy-4 -pregnene -3 ,11 , 20- t r ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
REACTION
2/3-OH
2/3-OH
2/3-OH
2/3-OH
Δ1
Δ1
Δ1
Δ1
l l a - O H
R E F .
L-496
L-496
L-496
L-496
K-465
K-465
K-465
K-465
S-849
S-825
S-825
M-587
M-587
M-587
444
T r a n s f o r m a t i o n s by Genus:
TABLE I I I
HAPLOSPORELLA HEBELOMA
HELICOBASIDIUM HELICOCERAS
HELICOSTYLUM
TAXONOMY
(Imperf. - Sphaeropsidales) (Basidio. - Agaricales) (Basidio. - T re me Hales) (Imperf. - Moniliales) (Phyco. - Mucorales)
SPECIES SOURCE SUBSTRATE REACTION R E F .
HAPLOSPORELLA
spec ies Sear le (M-1086)
HEBELOMA
s map lz ans
HELICOBASIDIUM
mompa
HELICOCERAS
WURB (M-84)
FAKU
NARI
oryzae
HELICOSTYLUM
FRI
p i r i forme ATCC
ATCC 8992
4 -andros tene-3 ,17-d ione
4-pregnene-3 ,20-d ione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
17a, 21 -dihydroxy -4-pr egnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
21-hydroxy-4-pregnene-3,20-dione
17a ,21-dihydroxy-4 ,14 -pregnadiene-3 ,20-d ione
11/3,17a-dihydroxy-5a-pregnane-3 ,20-d ione
11/3,21 -dihydroxy-5a-pregnane-3 ,20-d ione
3a, 11/3,21-tr ihydroxy-5a-pregnane-3 ,20-d ione
l l / 3 ,17a ,21- t r ihydroxy-5a -pregnane-3 ,20-d ione
3a, 11/3,17a-trihydroxy-5/3-pregnan-20-one
1/3-OH
6/3-OH
7/3-OH
reac t ion not identified
D-165
D-165
D-165
R-778
S-849
S-849
S-849
8-OH(later shown M - 6 4 0 to be 9a-OH)
Δ14 -> 14a, 15a-oxide
9a-OH;ll /3-OH-> n-c=o 9a-OH; 11/3-CH—I n-c=o 9a-OH; 11/3-OH-n-c=o 9a-OH; llß-OH-^1 n-c=o |9a-OH; 11/3-OH— n-c=o
B - 66
H-342
H-342
H-342
H-342
H-342
TABLE I I I
T r a n s f o r m a t i o n s by G e n u s : HELICOSTYLUM
445
SPECIES SOURCE SUBSTRATE REACTION R E F .
p i r i forme ATCC-8992 3/3,11/3,17a-trihydroxy-5/3-pregnan-20-one
l l /3-hydroxy-5/3-pregnane-3,20-dione
19 -nor -4 -p regnene -3 ,20 -d ione
4 -p regnene-3 ,20-d ione
1 l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione ace ta te
11/3,17o-dihydroxy-4-pregnene-3,20-dione
11/3,21 -dihydr oxy -4 -pregnene -3 ,20-dione 21-aceta te
17α, 21 -dihydr oxy -4 -pregnene -3 ,20-dione
11/3,17a, 21- t r ihydr o x y - 4 - p r e g -nene-3 ,20-d ione 21-ace ta te
9α-OH; 11/3-OH -n-c=o 9a-OH;i l /3-OH —n-c=o 14a-OH
oxidation -products not identified
14α-OH
14-OH
9α-OH
8-OH (later shown to be 9a-OH)
14a-OH; 21-OAcl - 2 1 -OH
9a-OH; 21-OAc - 2 1 - O H
9a-OH;l l /3-OH - 1 1 - C = 0
9a-OH;l l /3-OH — 1 1 - C = 0 ; 2 1 -O A c - 2 1 -OH
6/3-OH
H-342
H-342
B-73
M-636
E-204; M-614
M-636
H-342
M-640
E-204
E-204
H-342
H-342
E-204: M-601;
9a-OH
11a-OH
14a-OH
M-636
E-204 M-601 M-609
9a-OH; 11/3-OH - 1 1 - C = 0 ; 21-OAc—21-OH
M-632 M-636
E-204; M-601; M-636
E-204; M-601; M-617; M-636
H-342
446
TABLE I I I
Transformat ions by Genus: HELICOSTYLUM
SPECIES
pi r i forme
species
SOURCE
ATCC-8992
IFO
NRRL
SUBSTRATE
9a- f luoro- l l /3 ,15^ , 17ö J 21 - t e t r a -hydroxy-4-pregnene-3 , 20-dione
9a - f luor o -11 ß, 1 la, 21 - t r ihy dr oxy-l , 4 -p regnad iene -3 ,20 -d ione
9a -f luor o -17a, 21 -dihydr oxy - 1 , 4 -p regnad iene -3 ,11 ,20 - t r i one
l i a , 21 -dihydroxy-4,17(20)-pregnadien-3-one
11/3,21-dihydroxy-4,17(20)-pregnadien-3 -one
17a, 21-d ihydroxy-4 ,14-pregna-d iene-3 ,20-d ione
11/3,17a, 21 - t r i hyd roxy - l , 4 , 6 -
17a, 21 -d ihyd roxy-1 ,4 ,6 -p regna -t r i e n e - 3 , 1 1 , 2 0 - t r i o n e
Diosgenin
Solasodine
Tomatidine
3ß, 14/3-dihydroxy-5ß-20(22)-cardenolide
Saponins (sapogenin glycosides)
REACTION
14a-OH
14a-OH
14a-OH
9a-OH; l l a - O H - 11-C = 0
9a-OH; 11/3-OH -» n-c=o
14
Δ -*14a,15a-oxide
9a-OH
14a-OH
9a-OH
14a-OH
7/3, l la-diOH
Ίβ,ΙΙα-άίΟΉ; 7/3-OH->7-C = 0
7β-ΟΗ
9a-OH
l l a - O H
7a-OH
9a-OH
7 a , l l a - d i O H
12/3-OH
16/3-OH
R E F .
N-669
N-669
N-669
H-342
H-342; H-344
ß - 6 6 ; S-865
G-301; G-302
G-301; G-302
G-301; G-302
G-301; G-302
H-368
H-368; H-369
S-791
S-791
S-791
S-791
S-791
S-791
N-651
N-651
K-478
pregnatr iene -3,20-dione
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus : HELMINTHOSPORIUM (imperf. - Monmaies)
447
SPECIES
avenae
br izae
buchloes
coices (coicis)
gramineum
1 *
i r r e g u l ä r e
kusanoi
l e e r s i i
SOURCE
FRI
NI
NIHJ
OIAB (H-9)
NI
OIAB (H-10)
CBS
NI
NI
NARI
CBS
NI
OIAB
NI
OIAB (H-20)
SUBSTRATE
17a, 21-dihydroxy-4-pregnene -3,20-dione
17«, 21 -dihydroxy-4 -pregnene -3,20-dione
1 7a, 21 -dihydroxy-4 -pregnene -3,20-dione
17a, 21 -dihydroxy -4 -p regnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17/3-hydroxy-4-estren-3-one
17a, 21 -dihydroxy -4-pregnene -3 ,20-dione
4 -pregnene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
11)3,17a, 21 - tr ihydroxy -4 -p reg -nene -3 ,20 -dione
17a ,21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
17j3-hydroxy-4-estren-3-one
17a, 21-dihydroxy-4-pregnene -3 ,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3 ,20-dione
17a, 21-dihydroxy-4-pregnene-3,20-dione
REACTION
—
-
-
14a-OH
-
oxidation -products not identified
10/3 -OH
14a-OH
6/3-OH; l l a - O H
possible side chain degrada-tion
-
1
Δ
1
Δ
-
6/3-OH
6/3-OH
oxidation -products not identified
6/3-OH; l l a - O H
6/3-OH
R E F .
S-849
S-849
S-849
K-460
S-849
K-460
D-153
D-153
S-849
K-465
S-849
K-460; K-465
K-465
K-465
S-849
D-153
S-849
K-460
S-849
K-460
448
TABLE I I I
T ransformat ions by Genus: HELMINTHOSPORIUM
SPECIES
lepochloae
maydis
nodulosum
oryzae
panici-meliacei (panici-mil iacei)
sat ivum
SOURCE
NI
OIAB(H-5)
OIAB1H-6)
OIAB(H-19)
NI
OIAB(H-18)
S
NI
OIAB(H-2)
OIAB(H-3)
IAM
NIHJ ( F - l - 4 0 )
OIAB(H-15)
SUBSTRATE
1 la, 21 -dihydr oxy -4 -pr egnene -3,20-dione
1 Ta, 21 -dihydr oxy -4 -pregnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydr oxy-4-pr egnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
4 -p regnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
17a, 21-dihydroxy-4-pregnene -3 ,20-dione
17a, 21-dihydr oxy-4-pregnene-3,20-dione
REACTION
l i a - O H
oxidation -products not identified
oxidation -products not identified
11a-OH
-
oxidation -produc ts not identified
-
-
6ß-OH
-
15α-OH
15/3-OH
7a,15j3-diOH
7/3,15/3-diOH
14a,15/3-diOH
15a-OH
-
oxidation -produc ts not identified
R E F .
S-849
K-460
K-460
K-460
S-849
K-460
S-849
S-849
K-460
K-460
T-1022
T-1022
T-1022
T-1022
T-1022
T-1024
S-849
K-460
TABLE I I I
T r a n s f o r m a t i o n s by Genus : HELMINTHOSPORIUM
449
SPECIES
se t a r i ae
s igmoideum
spec ies
SOURCE
NI
OIAB(H-8)
NIHJ(B-15)
NARI
OIAB1H-37)
OIAB(H-39)
OIAB(H-40)
OIAB(H-42)
MCC (1-39)
NIHJ(B-8)
NIHJ(B-36)
NIHJIB-37)
NIHJ(B-66)
NIHJ(B-69)
NIHJ(B-70)
NIHJ(B-74)
OIABÎH-12)
OIAB(H-13)
SUBSTRATE
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21 -dihydroxy-4 -pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21 -dihydroxy-4-pregnene -3 ,20-dione
4-pregnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21 -dihydroxy-4-pregnene -3 ,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-dihydroxy-4-pr egnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
17a, 21-dihydroxy-4-pregnene -3 ,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene -3 ,20-dione
17a, 21 -dihydroxy -4 -p regnene -3,20-dione
REACTION
l i a - O H
l i a - O H
-
-
l i a - O H
l i a - O H
6j3-OH; l i a - O H
11/3-OH
6ß-OH; l l a - O H
7a-OH
7a-OH
-
1
Δ
1
Δ
l l a - O H
-
• -
l l a - O H
-
R E F .
S-849
K-460
S-849
S-849
K-460
K-460
K-460
K-460
K-460
M-570
M-570
S-849
S-849
S-849
S-849
S-849
S-849
S-849
K-460
K-460
450
TABLE I I I
T r a n s f o r m a t i o n s by Genus : HELMINTHOSPORIUM
SPECIES SOURCE SUBSTRATE REACTION R E F .
species
t e r e s
t r i t i c i -vulgar is
tu rc icum
velur inum (velutinum)
zonatum
OIAß (H-16)
OIAB ^H-27)
S
OIAB (H-43)
NI
OIAB(H-25)
NIHJ
NIHJ(B-34)
NIHJ(B-51)
NIHJ(F-1-73) |
OIAB ÎH-11)
S (4068)
S
OIAB (H-30)
NARI
NIHJ
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
11/3,21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
17a, 21 -dihydroxy-4-pregnene -3 ,11 ,20- t r ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3 ,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
K-460
6/3, l la-diOH
1
Δ
6/3-OH; 14a-OH
6/3-OH
2ß-OH
Δ ->5/3-H
_
K-460
S-857
K-460
S-849
K-4j60
K-460
S-849
14a-OH
S-849
S-849
S-849
K-460
S-849
S-849; S-857
S-849; S-857
S-849; S-857
S-849; S-857
S-849; S-857
K-460
S-849
S-849
1
Δ
1
Δ
1
Δ
1
Δ
451
TABLE I I I
T r a n s f o r m a t i o n s by Genus: HELMINTHOSPORIUM HEMISPORA
HENDERSONIA
TAXONOMY
(Imperf. - Moniliales) (Imperf. - Sphaeropsidales)
SPECIES
zizaniae
HEMISPORA
rogosa
HENDERSONIA
a b e r r a n s
acicola
(in mixed culture with Aspergi l lus niger [ l i a -OH])
(in mixed cul ture with Tr ichoderma album [17a-OH])
herpotr icha
1 phragmi t i s
rubi
(in mixed cul ture with Tr ichoderma nigrovi rens [17a-OH])
(in mixed cul ture 1 with Stigmina
platani [11/3-OH])
SOURCE
NI
OIABÎH-4)
FRI
MCC
ATCC-2585
NRRL-2595
NRRL-2594
MCC
NRRL-2593
SUBSTRATE
4-pregnene-3 ,20-d ione
17a, 21 -dihydr oxy -4 -pre gnene -3,20-dione
l l / 3 , 17a ,21 - t r i hyd r oxy - 4 - p r eg -nene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r i one
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
1 l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
4 -pregnene-3 ,20-d ione
11/3 -hydroxy-4 -p regnene -3 ,20 -dione
11/3,17a-dihydroxy-4-pregnene-3,20-dione
17a-hydroxy-4-p regnene-3 ,20-dione
4 -pregnene-3 ,20-d ione
REACTION
oxidation -products not ideatified
1
Δ
-
1
Δ
Δ1
-
21-OH
21-OH
21-ΟΗ
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
R E F .
K-465
K-465
K-465
K-465
K-460
S-849
D-183
M-566
M-566
M-566
D-183
D-183
D-183
D-183; M-566
M-566
M-566
452
T r a n s f o r m a t i o n s by Genus:
TABLE I I I HISTOPLASMA
HORMODENDRUM HUMICOLA
HURODAKE HYALOPUS
HYDROGENOMONAS
TAXONOMY
(Asco. - Endomycetales) (Imperf. - Moniliales) (Imperf. - Moniliales) (Taxonomy Unclear) (Imperf. - Moniliales) (Schizo. - Pseudomonadales)
SPECIES
HISTOPLASMA
capsulatum
HORMODENDRUM
olivaceum
pedrosoi
vir ide
HUMICOLA
gr i sea (grisae)
HURODAKE
(Taxonomy Unclear)
HYALOPUS
nopporoensis
HYDROGENOMONAS
facilis
SOURCE
FRI
ATCC-13596
FRI
LED(Z-IO)
FRI
S (15)
FRI
ATCC-11228
SUBSTRATE
17a, 21 -dihydroxy -4 -p regnene-3,20-dione
17a, 21 -dihydroxy -4-pregnene -3 ,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
4 -andros tene-3 ,17-d ione (autotrophic)
17a, 21-d ihydroxy-4-pregnene-3,20-dione
(autotrophic and heterotrophic)
11/3,17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
17a, 21 -dihydroxy -4-pregnene -3 ,11 ,20- t r ione
(heterotrophic)
REACTION
-
15a-OH
-
15a-OH
-
6/3-OH; l l a - O H
6/3 -OH; l l a - O H
1 7 - C = 0 - » 17/3-OH
2 0 - C = O ^ 20/3-OH
2 0 - C = O -20/3-OH
2 0 - C = O -20/3-OH
R E F .
S-849
A-9; B-58
S-849
B-56
S-849
S-849
S-849
F-228
F-228
F-228
F-228
453
T r a n s f o r m a t i o n s by Genus·.
TABLE I I I
HYGROPHORUS HYPHOLOMA HYPOCHNUS HYPOMYCES
TAXONOMY
(ßas id io . - Agar icales) (Basidio. - Agar icales) (ßas idio . - Agar icales) (Asco. - Hypocreales)
SPECIES SOURCE SUBSTRATE REACTION
HYGROPHORUS
conicus
HYPHOLOMA
species
HYPOCHNUS
centrifugum
centrifugus
sasaki i
HYPOMYCES
aurant ius
haematococcus (var. cancr i - Ref. M-574)
AL(C-219)
NRRL-2471
S
TNAES
CBS
FAHU
IAM
CBS
OR
UC
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
17α, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
3£-hydroxy-4-andros ten-17-one
17a -ethyl -17/3 -hydr oxy -4 -andros ten-3-one
17/3-hydr oxy-17a-propy 1-4-andros ten-3-one
17a, 21-d ihydroxy-4-pregnene-3,20-dione
11/3,17a, 21 - t r ihydroxy -4 - p r eg -nene -3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17/3-hydroxy-4-estren-3-one
3/3-(N,N-dimethylamino)-5-conenine
5 a - p r e g n a n e - 3 , l l , 2 0 - t r i o n e
4 -p regnene-3 ,20-d ione
6 ß , l l a - d i O H
15a-OH
11a-OH
19-OH
19-OH
19-OH
19-OH
19-OH
11a-OH
16a-OH
3/3-N(CH3)2 -3-C = 0 : Λ 5 - Δ 4
17/3-Ac^ 17/3-OH
Δ
R E F .
S-825
D-191; M-568
S-849
S-849
S-869
S-869
S-869
S-869
S-870
S-849
S-849
D-149
D-148
M-574
F-251
454
TABLE I I I
TAXONOMY
(Schizo.
SPECIES
solani
INTESTINAL MICROORGANISMS
unidentified
IRPEX
consors
lacteus
ISARIA
farinosa
SOURCE
NG
human feces
r a t feces
IAM
FRI
IAM
FRI
IRPEX ISARIA
SUBSTRATE
17/3-hydroxy-4-androsten-3-one
17/3-hydroxy- 17a -methyl -4 -andros ten-3-one
17a, 21 -dihydr oxy -4 -pregnene -3,20-dione
17a, 21 -d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione
5-cholesten-3j3-ol (anaerobic)
5-cholesten-3/3-ol
7-cholestenol
5,7-choiestadien-3/3-ol
5 -st igmasten-3/3-ol
17α,21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
(ßas id io . - Agaricales) Imperf. - Moniliales)
REACTION
Δ1; 17/3-OH — 17a-oxa-17-
c=o 1
Δ
1
Δ
1
Δ
Δ ^ δ β - Η
Δ ^ δ β - Η
Δ5— 5/3-H
Δ ^ δ β - Η
-
11α-ΟΗ
6j3-OH;l la-OH
6/3-ΟΗ; l l a - O H ; 11/3-ΟΗ
R E F .
L-525
L-525
L-525
L-525
S-914
C-133
C-133
C-133
C-133
S-849
S-849
S-849
S-849
T r a n s f o r m a t i o n s by Genus: HYPOMYCES INTESTINAL MICROORGANISMS -
(Genera not Identified)
455
T r a n s f o r m a t i o n s by Genus:
TABLE I I I
KABATIELLA KAIGARADAKE KAWARADAKE
KLOECKERA LACTOBACILLUS
TAXONOMY
(Imperf. - Moniliales) (Taxonomy Unclear) (Taxonomy Unclear) (Imperf. - Moniliales) (Schizo. - Eubacter ia les)
SPECIES
KABATIELLA
phoradendr i
KAIGARADAKE
(taxonomy unclear)
KAWARADAKE
(taxonomy unclear)
KLOECKERA
apiculata
LACTARIUS
chysor rheus
vole mus
LACTOBACILLUS
brevis
(in mixed cul ture with Mycococcus sp. Δ1)
SOURCE
ATCC-11129
S(27)
S (16)
NRRL
AL(F-31)
AL(SS-15)
IFO(3345)
SUBSTRATE
4-pregnene-3 ,20-d ione
12a -me thy i -4 -p regnene -3 ,11 ,20 -t r ione
4 ,16-pregnad iene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
4-pregnene-3 ,20-d ione
4 -p regnene -3 , 20-dione
l l j 3 ,17a ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
REACTION
21-OH
21-OH
21-OH
6/3-OH; 11a-OH
6/3-OH
-
-
-
oxidation -products not identified
oxidation -products not identified
-
1
Δ
R E F .
L-498
L-498
L-498
S-849
S-849
M-587
M-587
M-587
S-825
S-825
1-428
1-428
456
TABLE I I I
T r a n s f o r m a t i o n s by Genus.· LACTOBACILLUS LENITZITES
LENTINUS LENTODIUM
LENZITES
TAXONOMY
(Taxonomy Unclear) (Basidio. - Agaricales) (Basidio. - Agaricales) (ffasidip. - Agarir.alfifi)
SPECIES
buchnen
(in mixed cul ture with Mycococcus sp. Δ1)
bulgaricus
(in mixed cul ture with Mycococcus sp. Δ1)
LENITZITES
betulina
sep ia r ia
s tyrac ina
tennis
LENTINUS
vulpinus
LENTODIUM
squamosum
LENZITES
abietina
SOURCE
IFO(3230)
IFO(3492)
IAM
IAM
IAM
IAM
AL (C-137)
AL (G-17)
C
SUBSTRATE
l l j 3 ,17a ,21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
l l / 3 ,17a ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
1 7a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
d, 1-21-hydroxy-4-pregnene-3,20-dione
21-hydroxy-4-p regnene-3 ,20-dione
REACTION
-
1
Δ
-
—
6/3-OH; 11a-OH
-
-
-
oxidation -products not identified
oxidation -produc ts not identified
d,l-*d-15j3-OH + 1
6j3-OH
15/3-OH
R E F .
1-428
1-428
1-428
1-428
S-849
S-849
S-849
S-849
S-825
S-825
W-1102
M-585
M-585
457
Transformat ions by Genus:
TABLE I I I
LENZITES LEPIOTA
LEPTOSPHAERIA LEUCOPAXILLUS
TAXONOMY
(Basidio. - Agaricales) (Asco. - Sphaeriales) (ßasidio. - Agaricales)
SPECIES
bebulina (betulina)
s tyrac ina
LEPIOTA
molybdites
p r o c e r a
rachodes
LEPTOSPHAERIA
1 maculans
1 (in mixed cul ture 1 with Curvular ia
lunata -[11/3-OH])
1 (in mixed cul ture 1 with Curvular ia
lunata -[llj3-OH -l l / 3 - O H - > l l - C = 0 ] )
LEUCOPAXILLUS
1paradoxus
SOURCE
S
FRI
AL(G-19)
ALIG-59)
NRRL-2368
FRI
WURB(M-44)
WURBIM-76)
C
AL(F-55)
SUBSTRATE
4-pregnene-3 ,20-d ione
17a-hydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
21 -hyd roxy - l , 4 -p r egnad i ene -3,20-dione
4 -pregnene-3 ,20-d ione
REACTION
-
6/3-OH
-
oxidation -products not identified
oxidation -products not identified
oxidation -products not identified
oxidation -products not identified
oxidation -products not identified
oxidation -products not identified
17a -OH
17a-OH
17a-OH
6j3, l la-diOH
R E F .
S-859
S-859
S-859
S-849
S-825
S-825
R-778
S-849
R-778
R-778
W-1107
W-1106
W-1106
S-825
i i a u c i na
458
T r a n s f o r m a t i o n s by G e n u s :
TABLE I I I LICHTHEIMIA
LOPHOTRIChUS LYCOPERDON LYOPHYLLUM
MACROSPORIUM MARASMIUS
MARGARINOMYCES
TAXONOMY
iPhyco0 - Mucorales) (Asco. - Sphaeriales) (Basidio. - Lycoperdales) (Basidio. - Agaricales) (Imperfo - Moniliales) (Basidio. - Agaricales) (Imperf. - Moniliales)
SPECIES
LICHTHEIMIA
corymbifera
r amosa
LOPHOTRICHUS
mart in i (used in mixed culture)
LYCOPERDON
umbrinum
LYOPHYLLUM
aggregatum
MACROSPORIUM
bataticoia
MARASMIUS
s iccus
MARGARINOMYCES
species
SOURCE
SSSR
SSSR
c
NRRL-2372
AL(SS-60)
FRI
AL(SS-21)
FRI
SUBSTRATE
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
not given
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
17a, 21 -dihy droxy -4 -pregnene -3,20-dione
4-pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
REACTION
l l a - O H ; 11/3-OH
11a-OH; 11/3-OH
17a-OH
oxidation -products not identified
oxidation -products not identified
2/3-OH
oxidation -products not identified
R E F .
E-224
E-224
W-1106; W-1107
R-778
S-825
S-849
S-825
S-849
459
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: MEDICAGO
MELANCONIALES MELANOSPORA METARRHIZIUM
MICROCOCCUS
(Spermatophyta - Rosales) (Imperf. - Melanconiales) (Asco. - Hypocreales) (Imperf. - Moniliales) (Schizo. - Eubacter ia les)
SPECIES
MEDICAGO (Plant-Alfalfa)
sat iva
TAXONOMIC ORDER MELANCONIALES
(genus not given)
MELANOSPORA
pa ras i t i ca (used in mixed culture)
METARRHIZIUM
anisopliae
spec ies
MICROCOCCUS
candidus
1 c i t reus
(in mixed cul ture with Mycococcus sp. Ax)
1 congloneratus
SOURCE
-
Lepetit (L-952)
C
NI
PD (M-2313)
IAM
IFO (3332)
IAM
SUBSTRATE
1 la, 21 -dihydr oxy -1 ,4 -pregna -d i e n e - 3 , 1 1 , 20-tr ione
17«, 21-dihydroxy-1 ,4 -p regna-d iene-3 ,20-dione
not given
6/3-hydroxy-3a, 5a-cvclopregnan-20-one
3/3-hydroxy-5-pregnen-20-one
1 6 α , 1 7 α , 2 1 - [ 3 , 1 , 1 - 2-pyrazolino] -4 -p regnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
11/3,17a, 21 - t r i hyd roxy-4 -p reg -n e n e - 3 , 20-dione
4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
REACTION
20-C=O -20a-OH
11a-OH
17a-OH
11a-OH
11a-OH
11a-OH
oxidation
-
-
-
oxidation
R E F .
L-526
T-990
W-1106; W-1107
K-483
K-483
M-593
1-414; 1-415
1-414; 1-415
1-428
1-428
1-414; 1-415 1-414; 1-415
460
TABLE I I I
Transformat ions by Genus: MICROCOCCUS
SPECIES
dehydrogenans (see a lso under genus - Flavo-bacter ium)
fiava
f la vu s
(in mixed cul ture with Mycococcus sp. A,)
lute us
lysodeikticus
pi l tonensis
pyogenus aureus
1 (in mixed cul ture with Mycococcus sp. A,)
SOURCE
NG
IAM
IFO (3242)
IAM
U9-2)
IAM
NG
IFO (3061)
SUBSTRATE
l , 3 ,5 (10 ) - e s t r a t r i ene -3 ,17 /3 -diol
5 -andros tene-3ß , 17/3-dioi
17a-ethinyl-5-androstene-3/3, 17/3-diol
3/3-hydroxy-5-androsten-17-one
3/3-hydroxy-5-pregnen-20-one
3/3-hydroxy -27 -nor - 5 -choles ten-25-one
4-pregnene-3 ,20-d ione
1 la, 21 -dihydr oxy -4 -pregnene -3,20-dione
11/3,17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
4-pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
5-cholesten-3/3-01 (sole carbon source)
l l / 3 ,17a ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
REACTION
17/3-OH — 1 7 - C = 0
Δ5->Δ4; 3/3-OH ^ 3 - C = 0
Δ5 Δ4; 3/3-OH ^ 3 - C = 0 ; 17/3-OH — 1 7 - C = 0
3/3-OI}-3-C = 0 ; Δ 5 ^ Δ
Δ 5 - Δ 4 ; 3/3-OH - 3-C = 0
3/3-OH-*3-C=0; A 5 A 4
Δ ^ Δ
Δ 5 - Δ 4 ; 3/3-OH -> 3 - C = 0
-
-
-
-
oxidation
—
oxidation
-
-
R E F .
M-546
E-212; E-217
E-217
C-84
A-14; E-213; E-214
E-214
E-214
1-414; 1-415
1-414; 1-415
1-428
1-428
1-414; 1-415
1-414; 1-415; S-849
1-414; 1-415
1-414; 1-415; S-849
T-1030
1-428
1-428
461
TABLE I I I TAXONOMY
Transformat ions by Genus: MICROCOCCUS MICROMONOSPORA (Schizo. - Actinomycetales)
SPECIES
roseus
species
subflavus
(in mixed cul ture with Mycococcus sp. - AJ
ureae
var ians
MICROMONOSPORA
1 chalcea
SOURCE
Takeda
ATCC-13553 (IFO-3769)
ATCC-13554
ATCC-13555
IAM
IFO(3062)
IAM
(S-4)
IAM
(P-93)
ATCC-10026
SUBSTRATE
l l / 3 ,17a ,21 - t r i hyd roxy-4 -pregnene-3 ,20-d ione
l l / 3 , 17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
l l ß , 1 7 a , 2 1 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
l l / 3 , 17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-dione
17o ,21-d ihydroxy-4-pregnene-3,20-dione
l l / 3 , 17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
17a,21 -dihydroxy -4 -pregnene -3,20-dione
4-pregnene-3 ,20-d ione
17o, 21 -dihydroxy-4-pregnene -3,20-dione
e s t r an -3 -one
5a -andros tan-3-one
17a-hydroxy-5a-andros tan-3-one
5a -andros tane-3 ,17-d ione
l l j3 -hydroxy-4-es t ren-3-one
4 -andros tene -3 ,17-d ione
4 ,6 -andros t ad iene -3 ,17 -d ione
5a-pregnan-3-one
5a-pregnane-3 ,11-d ione
5a-pregnane-3 ,20-d ione
REACTION
1
Δ
1
Δ
1
Δ
1
Δ
-
-
1
Δ
-
—
oxidation
x,4 A ', enol.
1 4
Δ ' 1 4
Δ '
Λ 1 ' 1
Δ1; enol. 1
Δ X
Δ
Δ 1 ' 4
1 4
Δ '
Δ 1 ' 4
R E F .
1-431
1-431
1-431
1-431
S-849
1-428
1-428
1-414; 1-415
1-414; 1-415; S-849
1-414; 1-415
1-414; 1-415; S-849
S-867
S-867
S-867
S-867
S-864
S-864
S-864
S-867
S-867
S-867
462
TABLE I I I
Transformat ions by Genus: MICROMONOSPORA
SPECIES
chalcea
SOURCE
ATCC-10026
SUBSTRATE
5a -p regnane -3 , 11 ,20- t r ione
5/3-pregnan-3-one
l l /3-hydroxy-5/3-pregnan-3-one
14a-hydroxy-5/3-pregnan-3-one
17a-hydroxy-5/3-pregnan-3-one
20-hydroxy-5/3-pregnan-3-one
5/3-pregnane-3,11-dione
5/3-pregnane-3,20-dione
l l /3-hydroxy-5/3-pregnane-3,20-dione
14a -hydr oxy -5/3-pregnane -3,20-dione
17a-hydroxy-5/3-pregnane-3,20-dione
21-hydroxy-5/3-pregnane-3,20-dione
11/3,21 -dihydr oxy -5/3-pregnane -3,20-dione
11/3,14a, 17a ,21- te t rahydroxy-5/3-pregnane -3 ,20-dione
5/3-pregnane - 3 , 1 1 , 2 0 - t r ione
17a-hydroxy-4-p regnene-3 ,20-dione
21-hydroxy-4-p regnene-3 ,20-dione
11/3,21-dihydr oxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
11/3,17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
11/3,14a, 17a, 21 - tetrahydroxy -4 -pregnene-3 ,20-d ione
17a, 21-dihydr oxy-14α, 15α-oxido-4-pregnene-3 ,20-d ione
REACTION
1 4
Δ ' 1 4
Δ '
A1 '* 1 4
Δ ' 1 4
Δ 1 4
Δ '
Λ 1 ' 4
A ' ' 4
1 , 4
Δ
A 1 '*
1 4
Δ
Δ4; Δ 1 ' 4
Δ 1 ' 4
Δ 1 ' 4
Δ ν
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
REF.
S-867
S-867
S-867
S-867
S-867
S-867
S-867
S-867
S-867
S-867
S-867
S-867
S-867
S-867
S-867
S-864
S-867
S-867
S-864
S-864; S-867
S-864
S-864
S-864
T A B L E I I I
Transformat ions by Genus: MICROMONOSPORA
463
SPECIES
chalcea
SOURCE
ATCC-10026
ATCC-12452
SUBSTRATE
11/3,17a,21-tr ihydroxy-14a, 15α-oxido-4-pregnene-3 ,20-d ione
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
17a, 21 -dihydroxy -4 -p regnene -3 ,11 ,20- t r ione
14a, 17a ,21 - t r i hyd roxy-4 -p reg -n e n e - 3 , 1 1 , 2 0 - t r i o n e
17a, 21-dihydroxy-4,9(11)-p regnad iene -3 , 20-dione
17a, 21-d ihydroxy-4 ,14-pregna-d iene-3 ,20-d ione
4 ,16-p regnad iene -3 ,20-d ione
5/3-bisnor-cholan-3-one
e s t r an -3 -one
5a-andros tan-3-one
17a -hy dr oxy - 5a -andr ostan -3 -one
5a -andros tan-3 ,17-d ione
17/3-hydroxy-4-est ren-3-one
4 -andros tene -3 ,17-d ione
4 ,6 -andros t ad iene -3 ,17 -d ione
5a-pr e gnan-3 -one
5a -pregnan-3 ,11-d ione
5a-pregnane-3 ,20-d ione
5a -p regnane -3 ,11 ,20 - t r i one
5/3-pregnan-3-one
11/3-hydroxy -5/3-pregnan-3 -one
14a - hy dr oxy - 5/3-pr e gnan - 3 - one
17a-hydroxy-5/3-pregnan-3-one
20-hydr oxy-5/3-pre gnan-3-one
5/3-pregnane-3,11-dione
5/3-pr egnane-3 ,20-dione
11 ß - hy dr oxy - 5/3 -pr e gnane -3,20-dione
REACTION
1
Δ
1
Δ 1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
A*'4
1 4 .
Δ ' ; enoi.
A ' ' 4
1 , 4
Δ
Λ 1 ' 4
Δ ; enol. 1
Δ 1
Δ
A 1 ' 4
Δ 1 ' 4
Λ 1 ' 4
1 4
Δ
Λ 1 ' 4
1 , 4
Δ
Λ 1 ' 4
A 1 ' 4
1 4
Δ ' 1 4
Δ ' 1 4
Δ ' 1 , 4
Δ
R E F .
S-864
S-864
S-864; S-867
S-864
S-864
S-864
S-864
S-867
S-867
S-867
S-867
S-867
S-864
S-864
S-864
S-867
S-867
S-867
S-867
S-867
S-867
S-867
S-867
S-867
S-867
S-867
S-867
464
TABLE I I I
Transformat ions by Genus: MICROMONOSPORA
SPECIES
chalcea
SOURCE
ATCC-12452
SUBSTRATE
14a -hydr oxy -5/3 -pregnane -3,20-dione
1 la -hydr oxy -5/3 -pregnane -3,20-dione
21-hydroxy-5/3-pregnane-3,20-dione
11/3,21 -dihydroxy - 5/3 -pregnane -3,20-dione
l l /3 ,17a ,21- t r ihydroxy-5/3-pregnane-3 ,20-d ione
11/3,14α,17α,21 - tetrahydroxy -5/3-pregnane-3,20-dione
5/3-pregnane-3,11,20- t r ione
17a, 21 -dihydr oxy -5/3 -pregnane -3 ,11 ,20- t r ione
17a-hydroxy-4-pregnene-3 ,20-dione
17a, 21 -dihydr oxy -4 -pregnene -3,20-dione
11/3,17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
9a-f Iuoro- l l /3 ,17a , 21-tr ihydroxy -4-pregnene-3 ,20-d ione
11/3,14a, 17a, 21-tetrahydroxy -4-pregnene-3 ,20-d ione
17a, 21-dihydroxy-14α, 15α-oxido-4-pregnene-3 ,20-d ione
11/3,17a, 21- t r ihydroxy-14a , 15a-oxido-4 -pregnene -3 ,20-dione
4 -p regnene -3 ,11 ,20 - t r i one
17a, 21-dihydroxy-4-pregnene -3 ,11 ,20 - t r ione
14a, 17a, 21 - t r ihydroxy-4 -p reg -n e n e - 3 , 11 ,20- t r ione
17a, 21-dihydroxy-4 ,9(11)-pregna-d iene-3 ,20-d ione
17a ,21-d ihydroxy-4 ,14-pregna-d iene-3 ,20-d ione
REACTION
1>4
Δ
1 4
Δ '
4 1 , 4
Δ ; Δ
A*'4
1 , 4
Δ
1 , 4
Δ
1 4
Δ
1 4
Δ '
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ 1
Δ
1
Δ
1
Δ
1
Δ
R E F .
S-867
S-867
S-867
S-867
S-867
S-867
S-867
S-867
S-864
S-864
S-864; S-867
S-864
S-864
S-864
S-864
S-864
S-864; S-867
S-864
S-864
S-864
•
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus:
MICROMONOSPORA MILAN YEAST
MONILIA MONILIALES
MONOSPORIUM MORCHELLA MORTIELLA
(Imperf. - Moniliales) (imperf. - Moniliales) (Imperfo - Moniliales) (Asco. - Pez iza les ) (Taxonomy Unclear)
SPECIES
chalcea
spec ies
MILAN YEAST (See under genus Saccharomyces)
MONILIA
spec ies
TAXONOMIC ORDER MONILIALES
(genus not given)
MONOSPORIUM
apiospermum
MORCHELLA
c r a s s i p e s
MORTIELLA 1 (Taxonomy Unclear)
pusi l la
SOURCE
ATCC-12452
NG
NG
NRRL
Lepetit (L-1465)
FRI
NRRL-2369
FRI
SUBSTRATE
4 ,16-pregnad iene-3 ,20-d ione
5 ß -b isnor - cholan - 3 - one
5-cholesten-3/3-01 (sole carbon source)
24 /3-methyl -5 ,7 ,22-choles ta t r ien-3/3-01 (sole carbon source)
3/3-hydroxy-5-androsten-17-one
plant saponins
17a, 21 -d ihydroxy-1 ,4 -p regna -diene - 3 ,2 0 -dione
1 la, 21 -dihydr oxy -4 -pr egnene -3 ,20-dione
4 -p regnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
REACTION
Δ1
Δ 1 ' 4
uti l ization
util ization
3/3-OH-»3-C=0: A 5 A 4
Δ —>Δ
-
11α-OH; 14α-OH
-
oxidation -products not identified
6/3-OH
R E F .
S-864
S-867
S-793c
S-793c
M-552
K-478
T-990
S-849
R-778
S-849
465
466
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus : MORTIERELLA (Phyco. - Mucoraies)
SPECIES
MORTIERELLA
alpina
bainier i
*
candelabrum *
isabell ina
marburgens i s
*
oligospora
polycephala *
*
pusi l ia
*
tuberosa
*
SOURCE
ATCC-8979
CBS
CBS
CBS
NRRL
CBS
NRRL
CBS
CBS
CBS
SUBSTRATE
1,3, 5(10)-estratr iene-3,17/3-01
3 - h y d r o x y - l , 3 , 5 ( 1 0 ) - e s t r a t r i e n -17-one
4-pregnene-3 ,20-d ione
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
9a- f luoro- l l /3 ,17o ,21 -trihydroxy-4-pregnene-3 ,20-d ione
9a- f luoro- l l /3 , 17a,21-tr ihydroxy-4-pregnene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
4 -pregnene-3 ,20-d ione
9a- f iuoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4-dehydr otigogenone
11/3,17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
9a - f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
1 lö -hyd roxy-4 -p regnene -3 ,20 -dione
9a- f luoro- l l /3 ,17a , 21- t r ihydroxy-4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
9a- f Iuoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
REACTION
6/3-OH
6/3-OH; 1 7 - C = 0 -»17/3-OH
6/3-OH
6/3-OH
14-OH
6β-ΟΗ
1ξ-ΟΗ
1ξ-ΟΗ
---
6/3-ΟΗ
Ιξ-ΟΗ
---
6/3-ΟΗ
Ιξ-ΟΗ
6/3-ΟΗ
6/3-ΟΗ
Ιξ-ΟΗ
6/3-ΟΗ
Ιξ-ΟΗ
R E F .
L-493; L-497
L-493
L-495
F-239
F-237
F-239
F-237
F-237
M-587
M-587
M-587
F-239
F-237
M-587
M-587
M-587
F-239
F-237
F-239
F-239
F-237
F-239
F-237
TABLE I I I
467
T r a n s f o r m a t i o n s by G e n u s : MORTIERELLA MUCOR
TAXONOMY
(Phyco. - Mucorales)
SPECIES
zonata
*
*
MUCOR
adr ia t icus
adventit ius
angulisporus
berol inensis
buntingii
chr i s t i anens i s
c i rc inel lo ides
1 corymbifer
SOURCE
ATCC-13309
SSSR
UC
SSSR
SSSR
SSSR
UC
SSSR
FAR MIT
SUBSTRATE
4 -p regnene-3 ,20-d ione
1 l a -hyd roxy -4 -p regnene -3 ,20 -dione
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
9a - f luoro- l l j3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
9a- f luoro- l l /3 ,16a , 17a, 2 1 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
4 -pregnene-3 ,20-d ione
17a-hydroxy-4-pregnene-3 ,20 -dione
21-hydroxy -4 -p regnene-3 ,20-dione
17a,21 -d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
4 -p regnene-3 ,20-d ione
REACTION
6/3-OH
6/3-OH
6j3-OH
6/3-OH
1ξ-ΟΗ
1ξ-ΟΗ
6/3-OH; l l a - O H
11-OH
11-OH
11-OH
11-OH
6j3-OH;l la-OH
6/3-OH
6/3-OH
(8-OH) rev i sed 9a-OH
6/3-OH
6/3,14a-diOH
products of un-known or questionable s t ruc tu re
unknown
R E F .
F-239
F-239
F-239
F-239
F-237
F-237
E-224
M-601; M-636
M-601; M-636
M-601; M-636
M-601; M-636
E-224
E-224
E-224
M-640
E-224
C-82
C-82
C-82
468
TABLE I I I
T r a n s f o r m a t i o n s by Genus: MUCOR
SPECIES
dimorphosporus
d i spe r sus
dubius
e rec tus
geaevensis
globosus
glomerula
g r i seo cyanus
gr iseo cyanus (+)
SOURCE
SSSR
UC
UC
SSSR
SSSR
UC
SSSR
UC
ATCC-1027
ATCC-1207a
SUBSTRATE
1 7a, 21 -dihydr oxy -4 -pregnene -3,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
4 -pregnene-3 ,20-d ione
17ö-hydroxy-4-pregnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a,21 -d ihydroxy-4-pregnene-3,20-dione
17«, 21-dihydr oxy-4-pregnene-3,20-dione
4-pregnene-3 ,20-d ione
17a-hydroxy-4-p regnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene-3,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
17/3-hydroxy-4-androsten-3-one
4 -pregnene-3 ,20-d ione
21-hydroxy-4 -p regnene-3 ,20-dione acetate
17/3-hydroxy - 4 - e s t r e n - 3 -one
17/3-hydroxy-4-androsten-3-one
REACTION
6j3-OH
(8-OH) rev i sed 9α-OH
oxidation
oxidation
oxidation
oxidation
6β-ΟΗ;11α-ΟΗ
6/3-ΟΗ;11α-ΟΗ; l l ß - O H
11-OH
11-OH
11-OH
(8-OH) rev i sed 9a-OH
11-OH
6/3-OH; l l a - O H ; 11/3-OH
(8-OH) r ev i s ed 9a-OH
14a-OH
14a-OH
14a-OH; 21-OAc -»21 -OH
21 -OAc-21 -OH
14a-OH
14a-OH
R E F .
E-224
M-640
M-601; M-636 M-601; M-636
M-601; M-636
M-601; M-636
E-224
E-224
M-601; M-636
M-601; M-636
M-601; M-636
M-640
M-601; M-636
E-224
M-640
E-204
E-204
E-204
E-204
M-610; M-634
M-610; M-634
TABLE I I I
T r a n s f o r m a t i o n s by Genus : MUCOR
SPECIES
griseo-cyanus (+)
g r i seo-cyanus (-)
1 guil l iermondii
1 h iemal is
1 (var. albus)
SOURCE
ATCC-1207a
ATCC-1207b
AY
SSSR
ATCC-8690
ATCC-6800
NRRL-2684
SSSR
SUBSTRATE
19-nor -4 -p regnene -3 ,20 -d ione
4 -p regnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
21 -hydroxy-4 -ü regnene -3 ,20 -dione ace ta te
17a ,21-d ihydroxy-4 ,14-p regna-d iene-3 ,20-d ione
3j3-hydroxy-14a-5,20(22)-cardadienolide ace ta te
4 -p regnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
4 -p regnene-3 ,20-d ione (using spores)
6a- f luoro-17a ,21-d ihydroxy-16a-methyl -4 -pregnene -3 ,20 -dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
17a, 21 -dihydr oxy-4-p regnene-3,20-dione
REACTION
oxidation
11-OH
14a-OH
11-OH
(8-OH) r ev i sed 9a-OH
7a-OH
7a,14a-diOH
14a-OH
14a-OH;21-OAc - 2 1 - O H
14 Δ —14a, 15a-oxide
7a-OH; 3j3-OAc —3/3-OH
11-OH
11-OH
14a-OH
llj3-OH
6/3-OH
11-OH
11-OH
6/3,14a-diOH
7a,14a-diOH
6/3-OH
R E F .
M-601; M-636
M-601; M-636
M-601; M-636; M-614
M-601; M-636
M-640
C-94
C-94
M-601; M-635; M-636
M-635
B-66; S-865
C-95
M-601; M-636
M-601; M-636
S-835; V-1048
V-1042a
E-224
M-601; M-636
M-601; M-636
D-177
D-177
E-224
469
470
TABLE I I I
Transformat ions by Genus: MUCOR
SPECIES
hie m a u s
humicoia (humicolus)
humilis
hypochninus
javanicus
mandshur icus
mic rosporus
mucedo
SOURCE
uc
SSSR
SSSR
SSSR
NI
SSSR
UC
SSSR
UC
ATCC-7941
ATCC-9635
ATCC-9836
FRI
NI
SUBSTRATE
21-hydroxy-4 -p regnene-3 ,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
1 7a, 21 -dihydroxy -4-pregnene -3,20-dione
1 7Ö , 21 -dihydroxy -4 -pregnene -3,20-dione
4 -pregnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
3/3,14/3-dihydroxy-5/3-20(22)-cardenoiide
14/3-hydroxy-3-keto-5/3-20(22)-cardenoiide
17a, 21-dihydroxy-4-pregnene -3,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
17a, 21 -dihydroxy -4 -p regnene-3,20-dione
4 -pregnene-3 ,20-d ione
17a-hydroxy-4-pregnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
REACTION
(8-OH) rev ised 9a-OH
6/3-OH
6/3-OH
6/3-OH
6/3, l la-diOH
6/3-OH; 11a-OH; 14a-OH
3/3-OH->3-C = 0 ; l/3-OH;7/3-OH; 1/3,7/3-diOH; 5j3,7/3-diOH
7/3-OH
6/3-OH
(8-OH) rev ised 9a-OH
6/3-OH; 11a-OH
oxidation
oxidation
oxidation
oxidation
11-OH
11-OH
11-OH
6/3-OH;lla-OH
6/3,1 l a -diOH
R E F .
Μ-640
E-224
E-224
E-224
N-682
N-682
N-682
N-682
E-224
Μ-640
E-224
M-601; M-636
M-601; M-636
M-601; M-636
M-601; M-636
M-601; M-636
M-601; M-636
M-601; M-636
S-849
N-682
TABLE I I I
471
T r a n s f o r m a t i o n s by Genus : MUCOR
SPECIES
mucedo
murorum
pa ras i t i cus
1 *
SOURCE
NI
SSSR
UC
VEB
SSSR
ATCC-6476
SUBSTRATE
17a, 21 -dihydroxy-4-pregnene -3,20-dione
3/3,14/3-dihydroxy-5ß-20(22)-cardenoiide
14/3-hydroxy-3 -keto-5/3-20(22) -cardenolide
17a ,21-d ihydroxy-4-pregnene-3,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
4 -pregnene-3 ,20-d ione
1 7a, 21 -dihydr oxy -4 -pregnene -3 ,20-dione
4 -pregnene-3 ,20-d ione
19-nor -4 -p regnene-3 ,20-d ione
17a-hydroxy-4-p regnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione aceta te
1 la, 21 -dihydr oxy -4 -pregnene -3,20-dione
17a ,21-d ihydroxy-4 ,14-p regna-d iene-3 ,20-d ione
REACTION
6j3-OH;l la-OH
7j3-OH
7/3-OH
6/3-OH;l la-OH
(8-OH) r ev i sed 9α -OH
6ß,14a-diOH
6ß-OH
11α-OH
14α-OH
oxidation
11-OH
11-OH
unknown
9a-OH;21-OAc - 2 1 - O H
14a-OH
products of unknown or questionable s t ruc tu re
unknown
6j3-OH
11a-OH
14a-OH 14
Δ — 14a, 15a-oxide
R E F .
N-682
N-682
N-682
E-224
M-640
S-811
E-224
M-601
E-204; 1-424; M-601; M-614; N-682
M-636
M-601
M-601
T-980
M-640
T-980
T-980
T-980
N-682
M-601; N-682
N-682
B-66; S-865
472
TABLE I I I
T r a n s f o r m a t i o n s by G e n u s : MUCOR
SPECIES
pa ras i t i cus
*
* * *
*
*
pi r i fo rmis
plumbeus
SOURCE
ATCC-6476
SSSR
NRRL
SSSR
UC
SUBSTRATE
14/3-hydroxy-3-keto-5/3-20(22)-cardenolide
3a, 14/3-dihydroxy -5/3-20(22)-cardenolide
3j3,14j3-dihydroxy-5/3-20(22)-cardenolide
(Ref. N-683-acce le ra t ion of hydroxylation by pre incuba-tion with 4 - p r e g n e n e - 3 , 2 0 -dione)
3ß, 14/3-dihydroxy-17a-20(22)-cardenolide
21 -hydroxy-4 -p regnene-3 ,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
Sarsasapogenin
Diosgenin
4-dehydr otigogenone
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
REACTION
3 -C=0-* 3a-OH
3 - C = 0 -3/3-OH
5/3-Η-Δ4
(via 5/3-OH)
3 α - Ο Η -3 - C = 0
1/3-OH
5/3-OH
7/3-OH
1/3,7/3-diOH
5/3,7ß-diOH
3 /3 -OH-3 - C = 0
3/3-OH— 3 - C = 0 ; 5/3-Η-Δ4
5/3-OH
3/3-OH-> 3 - C = 0
(8-OH) rev i sed 9a-OH
6/3-OH; l l a - O H
6/3-OH
oxidation
R E F .
N-682 N-678
N-678
N-682
N-681
N-682
1-423; N-678; N-682; N-683
N-678; N-682; N-683
N-682
N-682
N-678; N-682
N-678
N-681
N-681
M-640
E-224
M-587
M-587
M-587
E-224
M-601; M-636
TABLE I I I
T r a n s f o r m a t i o n s by Genus: MUCOR
SPECIES
plumbeus
pusi l ius
r a c e m o s u s
1 ramannianus
rouxii
1 rouxianus
SOURCE
UC
SSSR
NI
SSSR
UC
SSSR
UC
ATCC-4857
SSSR
SUBSTRATE
17a-hydroxy-4-pregnene-3,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
4 -p regnene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
14/3-hydroxy-3-keto-5/3-20(22)-cardenolide
3/3,14/3-dihydroxy-5/3-20(22)-cardenol ide
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
4-pr e gnene - 3,2 0 - dione
17a -hydroxy-4 -p regnene -3 ,20 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
4 -p regnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
REACTION
oxidation
oxidation
oxidation
6/3-OH; l i a - O H
l i a - O H ; 14α-ΟΗ; 6 ß , l l a - d i O H
6/3-OH; 11α-OH; 14α-OH
7/3-OH
7/3-OH; 1/3,7/3-diOH; 5/3,7/3-diOH; 3/3-OH-+3-C=0
6/3-OH
oxidation
oxidation
oxidation
(8-OH) rev i sed 9α-ΟΗ
oxidation
6/3-OH; l i a - O H
(8-OH) rev i sed 9a-OH
11-OH
11-OH
11a-OH
R E F .
M-601; M-636
M-601; M-636
M-601; M-636
E-224
N-682
N-682
N-682
N-682
E-224
M-601; M-636
M-601; M-636
M-601; M-636
M-640
M-601; M-636
E-224
M-640
M-601; M-636
M-601; M-636 1
E-224
473
474
TABLE I I I TAXONOMY
Transformat ions by Genus.· MUCOR MYCENA
MYCOBACTERIUM (Basidio. - Agaricales) (Schizo. - Actinomycetales)
SPECIES
rouxianus
simplex
solani
spec ies
sphaerosporoa
spinosus
stolonifer
va r ians
vuillemini
MYCENA
strobi l inoides
MYCOBACTERIUM
album
berol inense
SOURCE
uc
uc
uc
NRRL
UC
UC
UC
SSSR
SSSR
AL (SS-75)
NG
NG
P F
SUBSTRATE
4-pregnene-3 ,20-d ione
17a-hydroxy-4-p regnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
17a, 21 -dihydroxy - 4 -pregnene -3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
plant saponins
21 -hydroxy-4 -p regnene -3 ,20 -dione
21-hydroxy-4 -p regnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
1 7a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
4 -pregnene-3 ,20-d ione
5-choIesten-3/3-oI
5-cholesten-3/3-01
17ß-hydroxy-4-es t ren-3-one
4 -andros tene-3 ,17-d ione
4 ,6 -androstadiene -3 ,17 -dione
17a-hydroxy-4-p regnene-3 ,20-dione
REACTION
oxidation
oxidation
oxidation
oxidation
(8-OH) rev i sed 9a-OH
(8-OH) rev i sed 9a-OH
(8-OH) rev i sed 9a-OH
(8-OH) rev i sed 9a-OH
(8-OH) rev i sed 9a-OH
6/3-OH
oxidation -products not identified
util ization
utilization
degradation
Δ 1
Δ 1
Δ 1
Δ1
R E F .
M-601; M-636
M-601; M-636
M-601; M-636
M-601; M-636
M-640
M-640
K-478
M-640
M-640
M-640
E-224
E-224
S-825
S-916
M-594; M-595
T-952
S-873
S-873
S-873
S-873
TABLE I I I
Transformations by Genus: MYCOBACTERIUM
SPECIES
berol inense
(In sequential fermen-tation with Cur vu 1-a r i a sp . -[11/3-OH])
1 butyricum
SOURCE
PF
PF
SUBSTRATE
11/3,17a-dihydroxy-4-pregnene-3,20-dione
17ö, 21 -dihydr oxy -4 -pre gnene -3,20-dione
9 a - f l u o r o - l l ß , 1 7 a , 2 1 - t r i -hydroxy-4 -p regnene -3 ,20 -dione
11/3,14a, 17a, 21 - te t rahydroxy-4-pregnene-3 ,20-d ione
17a, 21-dihydr oxy-14α, 15α-oxido-4-pregnene-3 ,20-d ione
l l ß , 17a ,21- t r ihydroxy-14a , 15a-oxido -4 -pregnene -3 ,20-d ione
4 ,6 -pr egnadiene -3 ,20-d ione
1 7 a , 2 1 - d i h y d r o x y - 4 , 9 ( l l ) -pregnadiene -3 ,20-dione
4 -pregnene - 3 , 1 1 , 2 0 - t r ione
14a, 17a ,21 - t r ihydroxy-4 -p r e g n e n e - 3 , 1 1 , 2 0- t r ione
17a, 21 -dihydr oxy -4 -pregnene 3,20-dione
17/3-hydroxy-4-est ren-3-one
4 -andros tene -3 ,17-d ione
4, 6 -andros tad iene-3 ,17-d ione
17a -hydroxy-4 -p regnene -3 ,20 -dione
11/3,17a-dihydr oxy-4-pregnene-3,20-dione
17a, 21 -dihydr oxy -4 -pregnene -3 ,20-dione
9a- f luoro- l l j3 ,17a , 21 - t r i -hydroxy-4 -p regnene -3 ,20 -dione
l l ß , 14a, 17a, 21 - te t rahydroxy-4-pregnene-3 ,20-d ione
17a ,21-d ihydroxy-14a ,15a-ox ido-4-pregnene-3 ,20-d ione
REACTION
Δ1
Δ1
Δ1
Δ1
Δ 1
Δ1
Δ1
Δ1
Δ1
Δ1
Δ1
Δ1; enol.
Δ1
Δ1
Δ 1
Δ1
Δ1
Δ1
Δ 1
Δ 1
R E F .
S-873
S-873
S-873
S-874
S-873
S-873
S-873
S-873
S-873
S-874
S-868
• S-873
S-873
S-873
S-873
S-873
S-873
S-873
S-874
S-873
475
476
TABLE I I I
Transformat ions by Genus: MYCOBACTERIUM
SPECIES
butyricum
(in mixed cul ture with Curvular ia sp . -[11/3-OH])
cheionei
cholesterol icum
flavum
SOURCE
P F
U
NG
NG
IPB-390
SUBSTRATE
11/3,17ö, 21- t r ihydroxy-14a, 15α-oxido-4-pregnene-3 ,20-dione
4 ,6 -pregnad iene-3 ,20-d ione
17α, 21 -dihydroxy-4,9(11) -pregna-diene-3 ,20-dione
4 -pr egnene -3 ,11 ,20 - t r ione
14α, 17α, 21 - t r ihydroxy-4 -p reg -nene - 3 , 1 1 , 2 0 - t r ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
4-pregnene-3 ,20-d ione 20-cycloethyleneketal
5-choiesten-3/3-oi (sole carbon source)
5-cholesten-3j3-ol (sole carbon source)
17j3-hydroxy-4-androsten-3-one
4 -androstene -3 ,17 -dione
20/3-hydroxy-4-pregnen-3-one
4-pregnene-3 ,20-d ione
21-hydroxy-4-p regnene-3 ,20-dione
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
REACTION
Δ1
1
Δ 1
Δ
1
Δ 1
Δ
1
Δ
1
Δ
utilization
utilization
Δ1; 17/3-OH-» 1 7 - C = 0
1
Δ
Δ1; 1 7 - C = 0 - > 17/3-ΟΗ
Δ1; 17β-(20β-OH-21-H)-» 1 7 - C = 0
Δ;Πβ-(20β-O H - 2 1 - H ) -17/3-ΟΗ
Δ1; 1 7 / 3 - A c ^ 1 7 - C = 0
Δ1; 17/3-Ac — 17/3-ΟΗ
Δ1; 17/3-(20-C= Ο-21-ΟΗ) -* 1 7 - C = 0
1
Δ
Δ1; 2 0 - C = O -20/3-OH
R E F .
S-873
S-873
S-873
S-873
S-874
S-868
F-251
M-594
M-594; M-595; T-952
C-100
C-100
C-100
C-100
C-100
C-100
C-100
C-100
C-100
C-100
1
TABLE I I I
T ransformat ions by Genus: M Y C O B A C T E R I U M
477
SPECIES
flavum
fortuitum
1 friedmannii
SOURCE
IPB (390)
IMJ(SG-988)
P F
SUBSTRATE
17a,21-dihydroxy-4-pregnene-3,11,20-trione
17a, 21-dihydroxy -1,4-pregna-diene-3,11,20-trione
3a-hydroxy - 5a-andr ostan-17-one
3a-hydroxy-5/3-androstan-17-one
3j3-hydroxy-5-androsten-17-one
17j3-hydroxy-4-estren-3-one
4-androstene-3,17-dione
4,6-androstadiene-3,17-dione
17a-hydroxy-4-pregnene-3,20-dione
11β, 17α-dihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene-3,20-dione
REACTION
Δ1
Δ*;20-Ο=Ο-> 20/3-OH
20-C=O-20/3-OH
3a-OH—3-C=0, Δ4
3a-OH->3-C=Q Δ1'4
3a-OH-3-C=0; Δ Ι Μ .
9a-OH; rev. aldol. ; enol. ; 9-C=0-9^-OH
3a-OH^3-C=0; Δ4
3a-OH-3-C=0; Δ1 '4
3a-OH-^3-C=0; Δ1'4; 9a-OH; rev. aldol. ; enol. ; 9-C=0^9£-OH
Δ1; Δ 5 - Δ 4 ; 3/3-OH — 3-C=0
Δ 5 - Δ 4 ; 3/3-OH ^ 3 - C = 0
A 1. A 5 A 4·
Δ ; Δ - Δ ; 3/3-OH-»3-C=0; 9a-OH; rev. aldol. ; enol. ; 9-C=0-9£-OH Δ1; enol.
Δ1
1
A
A1
Δ 1
1
Δ
REF.
C-100; C-101
C-100; C-101
C-100
S-818
S-818
S-818
S-818
S-818
S-818
S-818
S-818
S-818
S-873
S-873
S-873
S-873
S-873
S-873
478
TABLE I I I
Transformat ions by Genus: MYCOBACTERIUM
SPECIES
friedmannii
(in mixed cul ture with Curvular ia sp . -[11/3-OH])
hyalinum
lacticola
SOURCE
P F
NG
ATCC-9626
ATCC-12297
NG
P F
SUBSTRATE
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
11/3,14a, 17a ,21- te t rahydroxy-4-pregnene-3 ,20-d ione
17a ,21-dihydroxy-14a ,15a-oxido-4-pregnene-3 ,20-d ione
l l /3 ,17a ,21- t r ihydroxy-14a ,15a-oxido-4-pregnene-3 ,20-d ione
4 ,6 -pregnadiene -3 ,20-dione
17a, 21 -dihydroxy -4 ,9 ( l l ) -p regna-d iene-3 ,20-d ione
4 - p r e g n e n e - 3 , l l , 2 0 - t r i o n e
14a, 17a, 21 - tr ihydroxy -4 -pr egnene -3 ,11 ,20 - tr ione
17a, 21-dihydroxy-4-pr egnene -3, 20-dione
5-cholesten-3/3-ol
17a, 21-dihydroxy-4-pr egnene -3, 20-dione
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
17a ,21-d ihydroxy-6a ,16a-d i -me thy l -4 -p regnene -3 ,11 ,20 -t r ione
5-cholesten-3/3-01 (Ref. T-952, T-1030 -sole carbon source)
17/3-hydroxy-4-estren-3-one
4 -andros tene-3 ,17-d ione
4 ,6 -andros tad iene-3 ,17-d ione
17a-hydroxy-4-pregnene-3 ,20-dione
11/3,17a-dihydroxy-4-pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3, 20-dione
REACTION
Δ
Δ
Δ
Δ
Δ
Δ
Δ
Δ1
Δ
utilization
Δ1; 2 0 - C = O -20/3-OH
1
Δ
1
Δ
utilization
Δ ; enol. 1
Δ 1
Δ 1
Δ
1
Δ
1
Δ
R E F .
S-873
S-874
S-873
S-873
S-873
S-873
S-873
S-874
S-868
S-916
S-945
T-1005
A-24; A-25
M-595; S-916; T-952; T-1030
S-873
S-873
S-873
S-873
S-873
S-873
TABLE I I I
T ransformat ions by Genus: MYCOBACTERIUM
479
SPECIES
lacticola
1 (in mixed cul ture with Curvular ia sp . -[11/3-OH])
1 luteum
phlei
1 (in mixed cul ture 1 with Curvular ia lunata
-NRRL-2380-[l l /3-OH
SOURCE
P F
NG
AMCY
ATCC-354
ATCC-10142
SUBSTRATE
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
l l / 3 , 14a ,17a ,21 - t e t r ahyd roxy -4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy-14a, 15a-oxido-4-pregnene-3 ,20-d ione
11β, 17α, 21- t r ihydroxy-14a , 15α-oxido-4-pregnene-3 ,20-d ione
4 ,6 -p regnad iene -3 ,20-d ione
17a ,21-d ihydroxy-4 ,9 ( l l ) -p regna-d iene-3 ,20-d ione
4 -pr egnene - 3 , 1 1 , 2 0 - t r ione
14a, 17a, 21 - tr ihydroxy -4 -pr eg -nene - 3 , 1 1 , 2 0 - t r ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
5-cholesten-3/3-ol
11 /3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
11/3,21 -dihydroxy -4 -p regnene -3,20-dione
6a, 9a -d ib romo- l l /3 ,17a , 21 - t r i -hy dr oxy -16 - me thy lene - 4 -p regnene-3 ,20-d ione
6a, 9a -d i f luoro- l l /3 ,17a , 2 1 - t r i -hydroxy -16 - mé thy lène-4-pregnene-3 ,20-d ione 2 1 -propionate
6a-fluoro -17a-hydroxy-21 -methyl-4 , 9 ( l l ) - p r e g n a d i e n e - 3 , 2 0 -dione
2a- f luoro-17a ,21-d ihydroxy-4-pregnene - 3 , 1 1 , 2 0 - t r ione
17a, 21 -dihydroxy-4-pregnene -3 ,20-dione
17/3-hydroxy-4-est ren-3-one
4 -andros tene -3 ,17-d ione
4 ,6 -androstadiene -3 ,17 -dione
REACTION
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ 1
Δ
1
Δ 1
Δ
1
Δ
utilization 1
Δ
1
Δ
1
Δ
Δ1; 21-OPr-> 21-OH
1
Δ
1
Δ
Δ1; 14α-ΟΗ
1
Δ ; enol. 1
Δ 1
Δ
R E F .
S-873
S-874
S-873
S-873
S-873
S-873
S-873
S-874
S-868
S-916
F-231
S-873
A-7
A-7
H-391
H-401
S-868
S-873
S-873
S-873
TABLE I I I
Transformat ions by Genus.· MYCOBACTERIUM
SPECIES
phlei
ranae
SOURCE
ATCC-10142
ATCC-12298
NG
P F
ATCC-110
SUBSTRATE
1 la -hydroxy-4-pr egnene-3 ,20-dione
11/3,17a-dihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
9a- f luoro- l l /3 ,17o,21- t r ihydroxy-4-pregnene-3 ,20-d ione
17a, 21-dihydroxy-14o, 15a-oxido-4-pregnene-3 ,20-d ione
11/3, 17a, 21 - t r ihydroxy-14a ,15a-oxido - 4 -pr e gnene - 3 , 2 0 - dione
4 ,6 -p regnad iene-3 ,20-d ione
d iene-3 ,20-dione
4 -p regnene -3 ,11 ,20 - t r i one
l l ß , 1 7 a , 2 1 - t r i h y d r o x y - 6 a , 1 6 a -dimethyl-4 -pregnene - 3 , 2 0 -dione
5-cholesten-3/3-ol (Ref. T-952 ,T-1030 -sole carbon source)
11/3,14α, 17a ,21- te t rahydroxy-4-pregnene-3 ,20-d ione
14a ,17a ,21 - t r i hyd roxy-4 -p reg -nene -3 ,11 ,20 - t r i one
17/3-hydroxy-4-estren-3-one
4 -andros tene-3 ,17-d ione
4 ,6 -andros tad iene-3 ,17-d ione
17a-hydroxy-4-pregnene-3 ,20-dione
11/3,17a-dihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene-3 ,20-dione
9a-f luoro- l l j3 ,17a , 21- t r ihydroxy-4-pregnene-3 ,20-d ione
REACTION
Δ
Δ
Δ
Δ
Δ
Δ
Δ
Δ
Δ
Δ
utilization
1
Δ
1
Δ
Δ ; enol. 1
Δ 1
Δ 1
Δ
1
Δ
1
Δ
1
Δ
R E F .
S-873
S-873
S-873
S-873
S-873
S-873
S-873
S-873
S-873
A-24; A-25
M-594; M-595; S-916; T-952; T-1030
S-874
S-874
S-873
S-873
S-873
S-873
S-873
S-873
S-873
480
17ö,21-dihydroxy-4,9(ll)-pregna-^
TABLE I I I
Transformat ions by Genus: MYCOBACTERIUM
481
SPECIES
ranae
(in mixed cul ture with Curvular ia sp. -[Πβ-ΟΗ|)
rhodochrous
SOURCE
ATCC-110
NC
P F
ATCC-12674
SQ(SC-2318)
SUBSTRATE
11/3, 14α, 17a ,21- te t rahydroxy-4-pregnene-3 ,20-d ione
17a,21-dihydroxy-14a,15a-oxido-4-pregnene-3 ,20-d ione
11/3,17a, 21 - t r ihydroxy-14a , 15a-oxido-4-pregnene-3 ,20-d ione
4 ,6 -p regnad iene -3 ,20-d ione
17a ,21-d ihydroxy-4 ,9 ( l l ) -p regna-d iene-3 ,20-d ione
4 -p r egnene -3 ,11 ,20 - t r i one
5-cholesten-3/3-ol
14a, 17a ,21 - t r i hyd roxy-4 -p reg -nene - 3 , 1 1 , 2 0 - t r ione
17a, 21-dihydr oxy-4-pregnene-3,20-dione
11/3,17a, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
17j3-hydroxy-4-androsten-3-one
5a-pregnane-3 ,20-d ione
5/3-pregnane-3,20-dione
4-pregnene-3 ,20-d ione
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
9a- f luoro- l l /3 ,16a , 17a, 2 1 - t e t r a -hydroxy - 4 - p r e g n e n e - 3 , 2 0 -dione
6a, 9a-d i f luoro- l l /3 ,16a , 17a, 2 1 -t e t r ahydroxy-4 -p regnene-3,20-dione
9a- f luoro- l l /3 ,16a , 17a, 2 1 - t e t r a -hydroxy-1 , 4 -pr egnadiene -3,20-dione
9a- f luoro- l l /3 ,17a ,20 /3 ,21- te t ra -hydroxy-1 ,4 -p r egnadiene -3 ,20-dione
REACTION
1
Δ
1
Δ
1
Δ
1
Δ 1
Δ
1
Δ
utilization 1
Δ
1
Δ
1
Δ
1
Δ 1 4
Δ ' 4 1 4
Δ ; Δ 1
Δ 1
Δ
1
Δ
20-C=O-20 /3 -OH
1
Δ
20-C=O-20 /3 -OH
A ^ H ; 2 0 - C = O -+20/3-OH
20/3-OH-20-C=O
R E F .
S-874
S-873
S-873
S-873
S-873
S-873
M-594
S-874
S-868
F-232
S-890
S-890
S-890
S-890
T-1002
G-296; S-890; T-1002
G-296
S-890
G-296
G-296
G-294
482
TABLE I I I
Transformat ions by Genus: MYCOBACTERIUM
SPECIES
rhodochrous
rubroper t inc tum [rhodochrous - J„ ßac t .
7 3 : , 15 (1957)]
salmonicolor
smegmat i s
SOURCE
SQ(SC-2318)
SQ(SC-2921)
WISC
SQ(SC-2753)
NG
NG
ATCC-278
ATCC-361
ATCC-12051
ATCC-12549
SUBSTRATE
9a-f luoro- l l /3 ,16α, 17α, 20/3,21-pen tahydroxy-1 ,4 -p regna-d iene-3 ,20-dione
5-choiesten-3/3-ol
4 -pregnene-3 ,20-d ione
9a- f luoro- l l /3 ,17a , 21 -trihydroxy-4-pregnene-3 ,20-d ione
17/3-hydroxy-A-nor-3-androsten-2-one
4 -pregnene-3 ,20-d ione
9a- f iuoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
(Ref. T-952 - sole carbon source)
5-cholesten-3/3-01 (sole carbon s o u r c e )
4 -pregnene-3 ,20-d ione
14a, 17a ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
11/3,14a, 17a, 21- te t rahydroxy-4-pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3 ,11 ,20- t r ione
14a, 17a, 21 - t r ihydroxy-4 -p reg -nene - 3 , 1 1 , 2 0 - t r ione
17/3-hydroxy-4-androsten-3-one
21-hydroxy-4 -p regnene-3 ,20-dione acetate
17α, 21 -dihydroxy- 4 -pregnene -3,20-dione 21-aceta te
REACTION
20/3-OH -» 20-C=O
Δ 5 ^ Δ 4 ; 3 β - Ο Η ^ 3 - C = 0
1
Δ 1
Δ
9a-OH;17/3-OH - 1 7 - C = 0
9a-OH 1
Δ
utilization
utilization
i Δ
1
Δ
1
Δ
2 0 - C = O -20/3 -OH
1
Δ
1
Δ
1
Δ
ι Δ
Δ ; 2 1 - O A c -21-OH
14α-OH; 21-OAc - 2 1 - O H
Δ ; 21-OAc — 21-OH
14α-OH; 21-OAc -> 21-OH
R E F .
G-294; G-296
T-1005
T-1005
T-1005
S-885
S-885
T-1005
S-916; T-952
T-952
S-873
S-872; S-873
S-873
S-873
S-873; S-874
S-873
S-873; S-874
S-873
S-873
S-873
S-873
S-873
r u b r um 5-cholesten-3i3-ol
TABLE I I I
Transformat ions by Genus: MYCOBACTERIUM
483
SPECIES SOURCE SUBSTRATE REACTION R E F .
smegmat i s IMJ(SC-98) 3a-hydroxy-5a-andros tan-17-one
3α -hydr oxy - 5/3 -andros tan -17 -one
3/3-hydroxy-5-androsten-17-one
4 -p regnene-3 ,20-d ione
3 a - O H - 3 - C = 0 ; Δ 4
3a-OH->3-C = 0 ; A l » *
9a-OH; 3a-OH - 3 - C = 0 ; Δ 1 ' 4 ; r ev . aidol. ; enol.
3 a - O H - 3 - C = 0 : Δ Ι Μ ; 9α-OH; r ev . aldoL ; enol . ; 9 - C = 0 - 9 4 - O H
3 a - O H - 3 - C = 0 ; Δ 4
3a-OH 3-C=0;
9a-OH; 3a-OH - 3 - C = 0 ; Δ 1 ' 4 ; r ev . a l do l . , enol.
3a-OH 1>4 .
3-C=0 ; Δ ; " 9α-ΟΗ; r ev . aldol. ; enol. ; 9 - C = 0 ^ 9 £ - O H
Δ5— Δ4; 3/3-OH ^ 3 - C = 0
Δ - Δ -3j3-OH +3-C=0
9α-ΟΗ; Δ1; Δ 5 - Δ 4 ; 3/3-OH ^ 3 - C = 0 ; r ev . aldol. ; enol.
Δ1; Δ 5 - Δ 4 ; 3 j 3 - O H - 3 - C = 0 ; 9a-OH; r ev . aldol . ; enol. ; 9 _ 0 = θ - 9 ξ - Ο Η
Δ4->5α-Η
3 - C = 0 ^ 3 a - O H ; Δ 4 - 5 α - Η
Δ1; 9α-ΟΗ; rev . aldol . : enol.
S-818
S-818
S-818
S-818
S-818
S-818
S-818
S-818
S-818
S-818
S-818
S-818
S-820
S-820
S-820
S-820
1
Δ
484
TABLE I I I
Transformat ions by Genus: MYCOBACTERIUM
SPECIES
smegmat i s
(in mixed cul ture with Curvular ia sp . - [ l lß-OHp
SOURCE
IMJ (SG-98)
NG
NRRL-B-ieo1?
P F
SUBSTRATE
4-pregnene-3 ,20-d ione
3/3-hydroxy-5-androsten-17-one
4 -pregnene-3 ,20-d ione
3a, 12a-dihydroxy-5ß-cholanic acid
3α, 7α, 12a-trihydroxy-5/3-cholanic acid
5-cholesten-3/3-ol (Ref. S-793C sole carbon source)
5-cholesten-3/3-01 succinate
24/3-methyl-5, 7 ,22-cho les ta -tr iene-3j3-ol
9a - f luoro - l l /3 ,17a ,21- t r ihydroxy-6α, 16α-dimethyl-4-pre gnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
REACTION
Δ1; 9a-OH; r ev . a idol. ; eno l . ; 9-C=0 - 9 ξ - 0 Η
Ä;17j3-Ac-»17-c=o 9α-ΟΗ; Δ1; r ev , aldol. ; eno l . ; 17/3-Ac ->17-C=0
17/3-Ac-»17-C = 0 ; Δ1; 9α-OH; r ev . aldoL; eno l . ; 9 - C = 0 ^ 9 ξ - Ο Η
degradation [ A , B ] t o C 1 3 H20Û3
degradation [ A , B j t o C 1 5 H2204
degradation [ A , B l t o C 1 5 Η « 0 3
utilization
pa r t i a l u t i l iza-tion
utilization
Δ 1
Δ1
R E F .
S-820
S-820
S-820
S-820
S-821
S-819
S-821
S-915
S-915
S-915
S-915
S-793c; S-915
S-915
S-793c
A- 24; A- 25
S-868
TABLE I I I
Transformat ions by Genus: MYCOBACTERIUM
485
SPECIES
smegmat i s
spec ies
Baci l lus megather ium ΜΑΊ)
*
thamnopheos
SOURCE
SQ(SC-1684)
NG
SSSR (193)
SSSR(B-5)
NG
P F
SUBSTRATE
9 a - f l u o r o - l l / 3 , 1 7 a , 2 1 - t r i -hydroxy-4 -p regnene -3 ,20 -dione
5-cholesten-3/3-ol
l l / 3 ,17a ,21 - t r i hyd roxy-4 -pregnene-3 ,20-d ione
17a,21 -d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione
17a, 20/3,21 - t r ihydroxy-4-pregnene-3 ,11-d ione 20/3,21-diacetate
17a, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r i one
5-choiesten-3/3-ol
17/3-hydroxy-4-est ren-3-one
4 -andros tene -3 ,17-d ione
4 ,6 -andros t ad iene -3 ,17 -d ione
17a -hydroxy-4 -p regnene -3 ,20 -dione
11/3,17a-dihydroxy-4-pregnene -3,20-dione
1 la. 21 -dihydroxy -4 -pregnene -3,20-dione
9 a - f l u o r o - l l / 3 , 1 7 a , 2 1 - t r i -hyd roxy-4 -p regnene -3 ,20 -dione
11/3,14a, 17a ,21- te t rahydroxy-4-p regnene-3 ,20-d ione
17a, 21-dihydroxy-14a, 15a-oxido-4-p regnene-3 ,20-d ione
11/3 ,17a ,21- t r ihydroxy-14a ,15a-oxido - 4 -pr e gnene - 3 ,2 0 - dione
4 , 6 - p r egnadiene-3 ,20-dione
I
REACTION
Δ1
3 / 3 - O H - 3 - C = 0 : Δ 5 - Δ 4
3 / 3 - O H - 3 - C = 0 ; Δ5->Δ4; 6-C = 0
cholesterol—* r ing A cleavage to C26H4403
1
Δ
Δ1
20/3-OAc^20/3-OH; 21-OAc-> 21-OH
2 0 - C = O - 2 0 / 3 -OH
util ization
Δ ; enol.
Δ1
Δ1
Δ1
Δ1
Δ1
Δ1
Δ1
Δ 1
Δ 1
Δ1
R E F .
T-1005
S-930; L-524
S-930
S-930
K-476
K-477
S-917
S-917
M-594
S-873
S-873
S-873
S-873
S-873
S-873
S-873
S-874
S-873
S-873
S-873
(in mixed culture with
486
TABLE I I I
Transformat ions by Genus: MYCOBACTERIUM
SPECIES
thamnopheos
(in sequential fe rmenta-tion with Curvular ia sp. [11/3-OHD tuberculos is (3CG-st ra in)
SOURCE
P F
IMJ
PF
SUBSTRATE
17a ,21 -d ihyd roxy -4 ,9 ( l l ) -pregnadiene-3 ,20-d ione
4 - p r e g n e n e - 3 , l l , 2 0 - t r i o n e
14a ,17a ,21 - t r i hydroxy-4 -p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
17a, 21-d ihydroxy-4-pregnene-3,20-dione
3a-hydroxy-5a-andros tan-17-one
3a-hydroxy-5/3-androstan-17-one
3ß-hydroxy-5-andros ten -17 -one
17j8-hydroxy-4-estren-3-one
4 -andr ostene -3 ,17 -dione
4 ,6 -andros tad iene -3 ,17-d ione
17a-hydroxy-4-p regnene-3 ,20-dione
11/3,17a-dihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
REACTION
Δ1
1
Δ
Δ1
Δ1
3 a - O H ^ 3 - C = 0 : Δ4
3 a - O H ^ 3 - C = 0 ; Δ 1 ' 4
3 a - O H ^ 3 - C = 0 : Δ 1 ' 4 ; 9a-OH; rev . aldol . ; enoliz. ; 9 - C = 0 - * 9 | - O H
3 a - O H - 3 - C = 0 ; Δ4
3 a - O H - » 3 - C = 0 : Δ 1 ' 4
3 a - O H - 3 - C = 0 ; Δ 1 ' 4 ; 9a-OH; rev . aldol. ; enol. ; 9 -C=0-*9£-OH
Δ1; Δ5->Δ4; 3/3-OH^3-C=0
Δ5-*Δ4; 3/3-OH ^ 3 - C = 0
Δ1; Δ 5 - Δ 4 ; 3/3-OH-+3-C=0; 9α-OH; rev . aldol. ; enol.; 9 - C = 0 - 9 | - O H
Δ ; enol.
Δ 1
Δ1
Δ1
Δ 1
Δ1
REF.
S-873
S-873
S-874
S-868
S-818
S-818
S-818
S-818
S-818
S-818
S-818
S-818
S-818
S-873
S-873
S-873
S-873
S-873
S-873
TABLE I I I
487
Transformat ions by Genus·. MYCOBACTERIUM MYCOCLADUS MYCOCOCCUS
TAXONOMY
(Phyco. - Mucorales) iSchizo. - Actinomycetales)
SPECIES
tuberculos is
(in sequential f e rmenta -tion with Curvular ia sp. [11/3-OH])
MYCOCLADUS
1 hyalinus
MYCOCOCCUS
1 species
SOURCE
P F
SSSR
ATCC-13556 (IFO-3574)
SUBSTRATE
9 a - f l u o r o - l l / 3 , 1 7 a , 2 1 - t r i -hydroxy-4 -p regnene -3 ,20 -dione
l l / 3 ,14a ,17a ,21 - t e t r ahydroxy-4-pregnene-3 ,20-d ione
17a, 21-dihydroxy - 14o, 15a-ox ido-4 -p regnene -3 ,20 -dione
l l j 3 ,17a ,21- t r ihydroxy-14a ,15a -oxido-4-pregnene-3 ,20-d ione
4 ,6 -pr egnadiene -3 ,20-dione
1 7 a , 2 1 - d i h y d r o x y - 4 , 9 ( l l ) -pr egnadiene-3 ,20-dione
4 -p r egnene -3 ,11 ,20 - t r i one
14a, 17a ,21- t r ihydroxy-4 -p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
17a, 21 -dihydroxy-4-pregnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
11/3,21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
l l / 3 ,17a ,21 - t r i hyd roxy-4 -pregnene-3 ,20-d ione
9a- f luoro- l l /3 ,17a , 21 - t r i -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r i one
REACTION
Δ1
1
Δ
1
Δ
Δ1
1
Δ 1
Δ
1
Δ 1
Δ
1
Δ
l l a - O H
Δ1
1
Δ
Δ1
l
Δ
Δ1
1
Δ
R E F .
S-873
S-874
S-873
S-873
S-873
S-873
S-873
S-874
S-868
E-224
1-429
1-429
1-429
1-429
1-429
1-429
TABLE I I I
Transformat ions by Genus: MYCOCOCCUS
SPECIES
spec ies
(in mixed cul ture with: Acetobacter acet i
IFO-3169
Acetobacter xylinum IFO-3174
Achromobacter liquidum IFO-3084
Aerobacter arogenus IFO-3321
Agrobacter ium tumefaciens IFO-3058
Baci l lus ce reus IFO-3466
Bacil lus c i rcu lans IFO-3029
Bacil lus pymilus IFO-3020
Bac te r ium mycoides IFO-3040
Erwinia carotovora IFO-3380
Escher ichia coli IFO-3043
Flavobacter ium flavescens IFO-3058
Lactobacil lus b rev is IFO-3345
Lactobacil lus buchneri IFO-3230
Lactobacil lus bulgaricus IFO-3492
Micrococcus c i t r eus IFO-3332 )
SOURCE
ATCC-13557 (IFO-3588)
IFO (AJ
SUBSTRATE
l l / 3 ,17a ,21 - t r i hyd roxy-4 -pregnene-3 ,20-d ione
REACTION
Δ1
1
Δ
Δ 1
Δ 1
Δ1
Δ 1
Δ1
Δ 1
Δ1
Δ1
Δ1
1
Δ
R E F .
1-429
1-428
1-428
1-428
1-428
1-428
1-428
1-428
1-428
1-428
1-428
1-428
1-428
1-428
1-428
1-428
1-428
488
TABLE I I I
T ransformat ions by Genus: MYCOCOCCUS
SPECIES
species (in mixed cul ture with Micrococcus flavus -IFO-3242
Micrococcus pyogenus - IFO-3061
Micrococcus sub-flavus- IFO-3062
Pseudomonas aeruglnosa-IFO-3505
Pseudomonas fragi -IFO-3458
Pseudomonas f luor-escens - IFO-3459
Pseudomonas g rav -eolens - IFO-3460
Pseudomonas sp. -TAKEDA - B - l , B - 6 , ß - 7 , ß - 9 , 3 - 2 4 , B - 2 9 , B - 3 4 , 3 - 3 6 , 3 - 3 8 , B - 3 9 , B - 4 4 , B - 4 9
1 Pseudomonas s t r i a -faciens - IFO-3309
Sarcina albida -IFO-3063
Sarcina lute a -IFO-3232
Ser ra t i a m a r c e s c e n s -IFO-3046
1 Vibrio pe rco lans -IFO-3348
Xanthomonas malvacerum - IFO-3383)
SOURCE
IFO
SUBSTRATE
l l / 3 ,17ö ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
REACTION
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
R E F .
1-428
1-428
1-428
1-428
1-428
1-428
1-428
1-428
1-428
1-428
1-428
1-428
1-428
1-428
489
490
TABLE I I I TAXONOMY
MYCOGONE T r a n s f o r m a t i o n s by Genus: ^ ^ £ * L L A
MYROTHECIUM NADSONL\
(Imperf. - Moniliales) (Schizo. - Pseudomonadales) (Asco. - Sphaericales) (Imperf. - Moniliales) (Asco. - Endomycetales)
SPECIES
MYCOGONE
jaepii
MYCOPLANA
bullata
dimorpha
MYCOSPHAERELLA
hori i
la tebrosa
MYROTHECIUM
ror idum
species
NADSONIA
fulvescens
SOURCE
FRI
NG
NRRL
TNAES
CBS
OR
AMCY
NRRL
NRRL
SUBSTRATE
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
5 -cholesten -3/3-ol (sole carbon source)
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
1 7 a , 2 1 - d ihydroxy-4-pregnene-3,20-dione
17/3-hydroxy-4-estren-3-one
17j3-hydroxy-4-estren-3-one
17a-ethyl-17/3-hydroxy-4-e s t r en -3 -one
3ß-hydroxy-16a ,17a-ox ido-5-pregnen-20-one
plant saponins
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
REACTION
l i a - O H
16/3 -OH
1 6 - C = 0 (via-16/3-OH)
16j3-OH
16/3-OH
l i a - O H
R E F .
S-849
T-1030
M-587
M-587
M-587
S-849
D-149
D-149
S-950
S-950
P-746
K-478
M-587
M-587
M-587
491
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: NAEMATOLOMA NAUCORIA
NEOCOSMOSPORA NEUROSPORA
(ßas id io . - Agaricales) (Basidio. - Agaricales) (AscOo - Hypocreales) (Asco. - Sphaeriales)
SPECIES
NAEMATOLOMA
subla tera t ium
NAUCORIA
confragosa
NEOCOSMOSPORA
1 vas infecta
NEUROSPORA
c r a s s a
SOURCE
AL(H-6)
VEB
A U C - 1 7 2 )
ATCC-12717
ATCC-10336
NG
WFEB(74)
SUBSTRATE
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
14o-hydroxy-4-p regnene-3 ,20-dione
4 -pregnene-3 ,20-d ione
5ß-pregnane-3 ,20-d ione
4 -pregnene-3 ,20-d ione
14a -hydroxy-4 -p regnene-3 ,20-dione
21-hydroxy-4-pr egnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione acetate
4 -pregnene - 3 , 1 1 , 2 0 - t r ione
4 -p regnene-3 ,20-d ione
5-choles ten-3ß-ol (sole carbon source)
24/3-methyl -5 ,7 ,22-nholes ta-tr iene-3/3-ol (sole carbon source)
21 -hydroxy-4 -p regnene -3 ,20 -dione
REACTION
oxidation -products not identified
6/3,14a-diOH
6/3-OH
6/3,17a-diOH
17/3-Ac^ 17/3-OH
17/3-Ac-> 17β-ΟΗ
17/3-Ac — 17/3-OH
17j3-(20-C=O-21-OH)-17 j3-OH
nß-(2o-c=o-21-OAc) ^17 /3 -OH
1 7 / 3 - A c -17j3-OH
X-OH
util ization
uti l ization
9a-OH
R E F .
S-825
S-811
S-811
S-825
S-881
S-881
S-881
S-881
S-881
S-881
M-601; M-624; M-636
S-793c
S-793c
S-937
492
TABLE I I I
Transformat ions by Genus: NEUROSPORA NIGROSPORA
TAXONOMY
(Imperf. - Moniliales)
SPECIES
sitophila
species
NIGROSPORA
oryzae
spec ies
SOURCE
ATCC-9278
FRI
Sear le (M-714J
ATCC-8667
ATCC-12771
FRI
ATCC-12773
SUBSTRATE
5ß-pregnane-3 ,20-d ione
4 -p regnene -3 ,20 -d ione
17a-hydroxy-4-pregnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4 ,16-pregnad iene-3 ,20-d ione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
4 -andros tene -3 ,17 -dione
17ß-hydr oxy-4-andros ten-3-one
4 -andros t ene -3 ,17 -dione
4-pregnene-3 ,20-d ione
21-hydroxy-4 -p regnene-3 ,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
16a ,17a -ox ido-4 -p regnene -3 ,20 -dione
17a-hydroxy-4-pregnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione acetate
17α, 21 -dihydroxy -4 -pregnene -3,20-dione
4-pregnene-3 ,20-d ione
REACTION
X-OH
X-OH
X-OH
X-OH
X-OH
X-OH
7a-OH
X-OH
X-OH
15a-OH
12|3,15a-diOH
X-OH
X-OH
X-OH
15/3-OH
15a-OH; 2 1 -OAc-*21-OH
6/3-OH; l i a - O H
X-OH
R E F .
M-601; M-624
M-601; M-624
M-601; M-624
M-601; M-624
M-601; M-624
M-601; M-624
S-849
T-1037
M-596
M-596
M-596
M-596
M-596
M-596
M-596
M-596
M-596
S-849
M-596
TABLE I I I
493
Transformat ions by Genus: NIGROSPORA J NOCARDIA
TAXONOMY
(SchizOo - Actinomycetales)
SPECIES
spec ies
sphaer ica
NOCARDIA (synonym - proac t ino-mycetes)
a s t é ro ïdes 1 (synonym for spec ies
blackwellii)
1 *
SOURCE
ATCC-12774
ATCC-12772
NI
ATCC-3308
ATCC-9970
SUBSTRATE
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
3a, 14/3-dihydroxy-5/3-20(22)-cardenolide
3/3,14/3-dihydroxy-5/3-17a-20(22)-cardenolide
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide
3/3,14/3,16/3-trihydroxy-5/3-20(22)-cardenolide
3/3,14/3,16/3-trihydroxy-5ß-20(22)-cardenolide 3-aceta te
3/3,14/3,16/3-trihydroxy-5/3-20(22)-cardenolide 16-acetate
3/3,14/3,16/3-trihydroxy-5/3-20(22)-cardenolide 3 , 1 6 -diacetate
2a-f luoro-17a, 21-dihydroxy-4-p regnene -3 ,11 -20 - t r i one
11/3,17a, 21-tr ihydroxy-5/3-pregnane-3 ,20-d ione
11/3,17a, 21 - t r ihydroxy-4 -p regnene-3 ,20-d ione
REACTION
15a-OH
X-OH
3a-OH-»3-C=0
3 a - O H ^ 3 - C = 0 ; 12ß-OH
3 /3-OH-3-C = 0
12/3-OH; 3/3-O H - 3 - C = 0
12/3-OH
3/3-OH -+3-C=0
3/3-OAc — 3/3-OH
3 / 3 - O H - 3 - C = 0
3/3-OAc^ 3 - C = 0 ; 16ß-OAc-> 16/3-OH
3/3-OAc — 3/3-OH; 16/3-OAc-> 16ß-OH
3/3 -OAC-+ 3-C = 0
3/3-OAc-* 3/3-OH
1
Δ
4
Δ
Δ 1
R E F .
M-596
M-596
N-681
N-681
N-6 81
N-677
N-677
N-677
N-677
N-677
N-677
N-677
N-677
N-677
H-401
S-939
S-939
494
TABLE I I I
T r a n s f o r m a t i o n s by Genus: NOCARDIA
SPECIES
as té ro ïdes (synonum for spec ies blackwellii)
*
aurant ia
*"
SOURCE
ATCC-9970
ATCC-10904
LED
SÇKSC-2626)
AMCY
ATCC-12674
SQ
SUBSTRATE
11/3,17a, 21 - t r ihydroxy- 16a -methyl -4 -pregnene-3 ,20-d ione
l l ß , 17a, 21- t r ihydroxy-6a , 16a-dimethy 1-4-pregnene - 3 , 2 0 -dione
11/3, 17a, 21 - tr ihydroxy -4 - p r e g -nene-3 ,20-d ione
5 - choie sten-3/3-01
9a - f iuoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
11/3,17a, 21- t r ihydroxy-4-pr eg -n e n e - 3 , 20-dione
(use of dr ied thalli)
17α, 21-d ihydroxy-4-pregnene-3, 20-dione
6a-fluor 0-11/3,16a, 17a, 21 - t e t r a -hydroxy - 9 a - m e t h y l - 4 - p r e g -nene-3 ,20-dione
9a- f luoro- l l /3 ,17a , 21 - tr ihydroxy -4 -pregnene-3 ,20-d ione
6a, 9a-di f luoro- l l /3 ,16a , 17a, 21 -te trahydroxy - 12a -methyl -4 -p regnene-3 ,20-d ione
6a, 12a-dif luoro- l l /3 ,16a, 17a, 21 -t e t r ahydroxy-4 -p regnene-3,20-dione
5-cholesten-3/3-ol
4 -choles ten-3 -one (use of cell free enzymes)
6a-chloro-12a- f Iuoro- l l /3 ,16α, 17α, 21 - tetrahydroxy -4 -pregnene -3,20-dione
6a-chloro-12a-f luor o - l 1/3,16a, 17a, 21- te t rahydroxy-4-pregnene -3,20-dione 16,17-acetonide
12a-chloro-6a- f luoro-16a , 17a, 21 -t r i h y d r o x y - 4 - p r e g n e n e - 3 , 1 1 , 20-tr ione
REACTION
1
Δ
1
Δ
1
Δ
utilization
Δ1
1
Δ
1
Δ
9α-OH
1
Δ
1
Δ
1
Δ
1
Δ
Δ5—Δ4; 3/3-OH ->3-C=0
1
Δ
1
Δ
1
Δ
1
Δ
R E F .
H-392
A-24; A-25
S-939
M-D95
T-1005
F-231
S-890; T-1005
P-740; S-898
F-260
T-1005
F-260
F-261
T-1005
S-890
F-261
F-261
F-261
4-pregnene-3,20-dione
TABLE I I I
Transformat ions by Genus: NOCARDIA
495
SPECIES
aurant ia
*
*
*
*
blackwellii (see a s t é r o ï d e s )
SOURCE
SQ(SC-2316)
SQ(SC-2317)
ATCC-6846 (Squibb-SC-1584)
UC
SUBSTRATE
4-pregnene-3 ,20-d ione
9 a - f l u o r o - l l / 3 , 1 7 a , 2 1 - t r i -hydroxy-4 -p regnene -3 ,20 -dione
5-cholesten-3/3-01
4 -pregnene-3 ,20-d ione
9o -fluoro-11/3,17a, 21 - t r i -hydroxy-4 -p regnene -3 ,20 -dione
5-cholesten-3/3-ol
17a, 21-d ihydroxy-5a-pregnane-3,20-dione
17a, 21 -dihydroxy -5a -pregnane -3 ,11 ,20 - t r ione
3a, 11/3,17a, 21- te t rahydroxy-5/3-pregnan-20-one
17a,21-dihydroxy-5/3-pregnane-3,20-dione
11/3,17a, 21 -tr ihydroxy-5/3-pregnane-3 ,20-d ione
3a ,17a ,21- t r ihydroxy-5 /3-pregnane-11 ,20-d ione
3a ,17a ,21- t r ihydroxy-5 /3-pregnane-11 ,20-d ione 2 1 -aceta te
3a ,17a ,21 - t r i hyd roxy-16a -methy 1-5/3-pregnane-11,20-dione 21-aceta te
3a ,17a ,21- t r ihydroxy-16/3-methyl-5 /3-pregnane-11,20-dione 21-aceta te
17α, 21-dihydroxy-5/3-pregnane-3 ,11 ,20 - t r ione 21-ace ta te
9 a - f l u o r o - l l / 3 , 1 7 a , 2 1 - t r i -hyd roxy-4 -p regnene -3 ,20 -dione
2a - f luoro- 17a, 21 -dihydroxy -4 -pregnene - 3 , 1 1 , 2 0 - t r i o n e
4 -p regnene-3 ,20-d ione 20-cycloethyleneketal
REACTION
Δ1
1
Δ
3/3-OH^3-C = 0
Δ1
1
Δ
Δ 5 - Δ 4 : 3 /3 -OH^3-C=0
Δ 1 ' 4
Δ 1 ' 4
Δ 1 ' 4 ; 3α -ΟΗ—3-C=0
Δ 1 ' 4
Δ 1 ' 4
Δ1'4; 3a -OH—3-C=0
Δ , 3a -OH—3-C=0 2 1 - O A c ^ 2 1 - O H
Δ 1 ' 4 ; 3a -OH->3-C=0
1>4
Δ ; 3a-OH — 3 - C = 0
Δ 1 ' 4 ; 21 -OAC-21-OH
Δ1
Δ1
Δ1
R E F .
T-1005
T-1005
T-1005
T-1005
T-1005
T-1005
S-939; S-943
S-943
S-943
S-939; S-943
S-939; S-943
S-943
S-939
S-902
S-905
S-939; S-943
T-1005
H-401
F-251
496
TABLE I I I
T r a n s f o r m a t i o n s by Genus: NOCARDIA
SPECIES
braz i l i ens i s *
coeliaca *
convoluta *
coral l ina
1
SOURCE
SQ(SC-2627)
SQ(SC-2751) (WC-704)
ATCC-4275
ATCC-999
SUBSTRATE
9a - f luo ro - l l / 3 ,17û ,21- t r ihy -d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
9ö - f luo ro - l l / 3 ,17a ,21 - t r ihy -d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
l l / 3 ,17a ,21 - t r i hyd roxy-4 -pregnene-3 ,20-d ione
17/3-hydroxy-4-estren-3-one (possible synonym -Myco-bac te r ium rhodochrous -Ref0 F-231 - use of dr ied thalii) (Ref., F-232 and H-399 -use of inhibitors)
4 - e s t r ene -3 ,16 -d ione
16a-hydroxy-4-es t ren-3 -one
16/3-hydroxy-4- e s t r en -3 -one
17/3-hydroxy-4-androsten-3-one
2a, 17/3-dihydroxy-4-androsten-3-one
2a, 17/3-dihydroxy-4-androsten-3-one diacetate
2/3, 17/3-dihydroxy-4-andr os ten-3-one diacetate
REACTION
Δ1
1
Δ
Δ1
Δ1; enoL ; 17j3-OH-> 1 7 - C = 0
Δ1; enoL
Δ1; enoL ; 16a-OH-+ 1 6 - C = 0
Δ ; enoL , 1 6 / 3 - 0 H -1 6 - C = 0
1
Δ
17/3-OH — 1 7 - C = 0
Δ1; 17/3-OH — 1 7 - C = 0
Δ1; 17/3-OH -1 7 - C = 0
Δ1; 2a-OAc-+ 2a-OH; 17/3-OAc->17-C=0
2a-OAc —2a-OH; 1 7 ß - O A c -1 7 - C = 0
Δ1; 2/3-OAc — 2/3-OH; 17/3-OAc->17-C=0
2/3-OAc — 2/3-OH; 17/3-OAc-*17-C=0
R E F .
T-1005
T-1005
S-939
F-231 H-399
S-793a
S-793a
S-793a
F-231 ; H-399"
F-231 ; H-399
F-231 ; H-399
H-399
F-231 ; H-399
H-399
H-399
H-399
TABLE I I I
Transformat ions by Genus: NOCARDIA
497
SPECIES SOURCE SUBSTRATE REACTION R E F .
coral l ina ATCC-999 4 -andros tene-3 ,17-d ione
9a-fluoro-11/3,16a, 1 7 a a - t r i -hydroxy -17a/3-hydroxy methyl -D -homo-4 -andros tene - 3 , 1 7 -dione
4-pregnene-3 ,20-d ione
l l /3 ,21-d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3 , 20-dione
9a -ch lo ro - l l /3 ,21 -d ihydroxy-4 -pregnene-3 ,20-d ione
9a- f luoro-7a , l l /3-dihydroxy-4-pregnene-3 ,20-d ione
9a -fluor o-11/3,21 -dihydroxy -4 -pregnene-3 ,20-d ione
7a, 11/3,21-tr ihydroxy-4-pregnene-3,20-dione
11/3,17a, 21 - t r ihydroxy -4 - p r e g -nene -3 ,20-dione
la -fluoro-11/3,17a, 21 - t r ihydroxy -4-pregnene-3 ,20-d ione
9a-f luoro-7a , 11/3,21-trihydroxy-4-pregnene-3 ,20-d ione
9a-fluoro-11/3,16a, 21- t r ihydroxy -4-pregnene-3 ,20-d ione
9a-fluoro-11/3,17a, 21 - t r ihydroxy-4-pregnene-3 ,20-d ione
l l /3 ,17a ,21- t r ihydroxy-2a-methy l -4 -pregnene-3 ,20-d ione 2 1 -aceta te
11/3 ,16a ,17a ,21- te t rahydroxy-4-pregnene-3 ,20-d ione
21 -OAc-21-OH
21-OAc^21-OH 1
Δ
F-231 ; F-232; H-399
S-910
F -231 ; F-232; H-399
F - 2 3 1 ; H-399
F -231 ; F-232; H-399
H-399
B-56
F - 2 3 1 ; H-399
B-56
F-230; F -231 ; F-232; H-399
F - 2 3 1 ; H-401
3-56
H-403
F - 2 3 1 ; K-399; H-403
F -231 ; H-399
H-399
B - 6 1 ; F - 2 3 1 ; H-399
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
498
TABLE I I I
T r a n s f o r m a t i o n s by Genus: NOCARDIA
SPECIES
coral l ina
*
*
*
NOTE: For source ATCC-4273 above - possibly Mycobacterium ag res t e and Mycobacterium rhodochrous - J . Gen. Microbio l . , 21 : 139
[(1959)
SOURCE
ATCC-999
ATCC-4273
ATCC-4275
ATCC-13258
SUBSTRATE
9 a - c h l o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 - t e t r a -hydroxy-4-pregnene-3 ,20-d ione
9 a - f l u o r o - l 4 , l l / 3 , 1 7 ö , 2 1 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione
9a-f luoro-6/3,11/3,170,21-tetra-hydroxy -4 -pregnene-3 ,20-d ione
9a- f luoro- l l /3 ,16a , 1 7 a , 2 1 - t e t r a -hydroxy-4 -p regnene-3 ,20-dione
9a-fluoro-11/3,16a, 1 7 a , 2 l - t e t r a -hydroxy-4 -p regnene-3 ,20-dione 16 ,21-diace ta te
9 a - f l u o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 - t e t r a -hydroxy-4-pregnene-3 ,20-d ione 16,17-acetonide
2 a , 9 a - d i f l u o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 -t e t r ahyd roxy -4 -p regnene -3 ,20 -dione 16,17-acetonide
9a-fluoro-6/3,11/3,16a, 17a, 21 -pen tahydroxy-4-pregnene-3 ,20-dione 16,17-acetonide
17a, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r ione
2a-f luoro-17a, 21-dihydroxy-4-pr egnene - 3 , 1 1 , 2 0 - t r ione
11/3,17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
4-pregnene-3 ,20-d ione
9a- f luoro- l l /3 ,17a , 21 - t r ihydroxy -4 -pregnene-3 ,20-d ione
5-choIesten-3/3-ol
4 -andros tene-3 ,17-d ione
19-hydroxy-4 -andros tene -3 ,17-dione
REACTION
1
Δ
—
1
Δ
1
Δ
1
Δ ; 1 6 a - O A c ^ 16a-OH;21-OAc - 21-OH
1
Δ
Δ1
1
Δ
1
Δ
Δ1
1
Δ
1
Δ 1
Δ
Δ5-*Δ4; 3/3-OH ^ 3 - C = 0
9a-OH; Δ1; r ev . aldol. ; enol.
1
Δ ; r e v e r s e aldol;
(Formaldehyde î ) enol.
R E F .
H-399
H-399
F-231
B - 6 1 ; F -231 ; H-399; O-704
B - 6 1 ; F-255; O-704
F-231 ; H-399
H-401
H-400
F -231 ; H-399
H-401; H-402
S-939
T-1005
T-1005
T-1005
M-597
M-597
TABLE I I I
499
T r a n s f o r m a t i o n s by Genus: NOCARDIA
SPECIES
coral i ina
*
erythropol is 1 (Mycobacterium 1 rhodochrous , J .
Bact. 73: 23,1957)
SOURCE
ATCC-13258
ATCC-13259
NG
ATCC-4277 (Squibb SC-
2820)
NCTC-2569
NG
SUBSTRATE
1 la, 21 -dihydroxy -4 -pr egnene -3,20-dione
4 -andros tene -3 ,17-d ione
19 -hydroxy-4 -and ros t ene -3 ,17 -dione
4 -p regnene-3 ,20-d ione
5-cholesten-3/3-01 (sole carbon source)
24/3 - methyl - 5 , 7 , 2 2 - cholesta -trien-3/3-ol (sole carbon source)
l l / 3 , 17a ,21 - t r i hyd r oxy - 4 - p r eg -nene-3 ,20-d ione
5-cholesten-3/3-ol (sole carbon source)
1 ,3 ,5(10)-es t ra t r ien-3 ,17/3-dio l
l , 3 , 5 ( 1 0 ) - e s t r a t r i e n - 3 , 1 6 a , 1 7 / 3 -t r io l
17/3-hydroxy-4-androsten-3-one
3 -hydr oxy - 5 -andr osten -17 -one
4 -p regnene-3 ,20-d ione
3a-hydroxy-5/3-cholanic acid
3α, 7α-dihydroxy-5/3-cholanic acid
3α, 12α -dihydroxy -5/3-cholanic acid
3α, 7α, 12α-trihydroxy-5/3-cholanic acid
5 -cholesten -3/3-ol ace ta te
5-cholesten-3/3-ol pa imi ta te
24/3-methyl-5, 7 ,22 -cho les t a t r i en -3/3-01 (sole carbon source)
REACTION
9a-OH
9a-OH; Δ ; r e v . aidol. ; enoL
9a-OH
1
Δ ; r ev . aldol; (Formaldehyde f )
enol.
9a-OH
9a-OH; 17/3 -Ac -»17/3-OH
utilization
util ization
1 Δ
utilization
-
-
util ization
utilization
util ization
-
-
util ization
util ization
-
util ization
util ization
R E F .
D-173
D-172; M-597
D-172; M-597
M-597
D-173
D-172
S-793c
S-793c
T-1005
M-595; S-793c
S-793c
S-793c
S-793c
S-793c
S-793c
S-793c
S-793c
S-793c
S-793c
S-793c
S-793c
S-793c
500
TABLE I I I
Transformat ions by Genus: NOCARDIA
SPECIES
farcinica
formica
*
gardner i * (see as téro ïdes)
globerula (Mycobacterium rhodo-c h r o u s - J . ßac t . 73: 24, 1957) *
*
i talica n. s.
leishmanii
*
SOURCE
NG (No. 1, 2)
NRRL-2470
ATCC-9604 (Squibb-SC-
1940) NCTC-6531
(Squibb - SC-6531)
NG
ATCC-9356
FAR MIT
ATCC-6855
SUBSTRATE
5-cholesten-3/3-ol (sole carbon source)
24/3-methyl -5 ,7 ,22-choles ta-trien-3/3-ol (sole carbon source)
l l /3 ,17a ,21- t r ihydroxy-5/3-pregnane-3 ,20-d ione
l l / 3 ,17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy-6a, 16a-dimethyl -4-pregnene -3,20-dione
9a-f luoro- l l /3 ,17α, 21 -trihydroxy-4-pregnene-3 ,20-d ione
9a- f luoro- l l i3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
5-cholesten-3/3-ol (sole carbon source)
24j3-methyl-5 ,7 ,22-choles ta-t r i en -3ß -o l (sole carbon source)
l l j3 ,17a,21- t r ihydroxy-5j3-pregnane-3 ,20-d ione
11)3,17a, 21 - t r ihydroxy-4-pregnene-3 ,20-d ione (Ref. B-37 - use of antibiotics^
9a- f luoro- l l j3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
l l j3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
9a - f iuoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
9a - f luoro- l l /3 ,17a ,21- t r ihydroxy-1,4 -pregnadiene -3 ,20-dione
11/3,17a, 21-trihydroxy-5/3-pregnane-3 ,20-d ione
l l j3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
9a-f luoro-17a, 21-dihydroxy-6a, 16a -dimethy 1-4 -pregnene -3 ,11 ,20- t r ione
REACTION
utilization
utilization
Δ4
1
Δ
1
Δ
1
Δ
1
Δ
utilization
utilization
Δ4
1
Δ
Δ1
16α-ΟΗ
16α-ΟΗ
16α-ΟΗ
16α-ΟΗ
Δ4
Δ1
Δ 1
R E F .
S-793c
S-793c
S-939
S-939
Α - 2 4 ; Α-25
Τ-1005
Τ-1005
S-793C
S-793C
S-939
β-37 S-939
Τ-1005
S-918
S-918
S-918
S-918
S-939
S-939
• Α-24; Α-25
501
TABLE I I I
Transformat ions by Genus: NOCARDIA
SPECIES
maculata
madurae *
mexicanus
minima
*
opaca
SOURCE
NG
SQ(SC-2628)
NG
ATCC-8674
ATCC-4276
SUBSTRATE
5-cholesten-3/3-ol (sole carbon source)
24 /3-methyl -5 ,7 ,22-choles ta t r ien-3/3-01 (sole carbon source)
9a -fluoro-11/3,1 la, 21 -tr ihydroxy-4-pregnene-3 ,20-d ione
5-cholesten-3/3-01 (sole carbon source)
24j3-methyl-5 ,7 ,22-choles ta t r ien-3/3-01 (sole carbon source)
l l j3 ,17a ,21- t r ihydroxy-5ß-p regnane -3 ,20 -d ione
11/3,17a, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
17/3-hydroxy-4-est ren-3-one
4 -andros tene-3 ,17-d ione
4 ,6 -andros t ad iene -3 ,17 -d ione
17a -hydroxy-4 -p regnene-3 ,20-dione
11/3,1 la- dihydroxy- 4 -pregnene -3,20-dione
17α, 21 -dihydroxy -4 -pregnene -3,20-dione
9a-f luoro-17a, 21-dihydroxy-4-pregnene-3 ,20-d ione
11/3 ,17a,21- t r ihydroxy-4- p r e g -nene-3 ,20-d ione (use of antibiotics)
17α, 21-dihydroxy-14α, 15α-oxido-4-pregnene-3 ,20-d ione
11/3,17α, 21- t r ihydroxy-14a , 15α-oxido-4-pregnene-3 ,20-d ione
l l ß , 1 4 a , 1 7 a , 2 1 - t e t r a h y d r o x y - 4 -pregnene-3 ,20-d ione
6 a , 9 a - d i f l u o r o - l l / 3 , 1 7 a , 2 1 - t r i -hydroxy -16-méthy lène-4-pregnene-3 ,20-d ione
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
2a- f luoro- l 7a, 21-dihydroxy-4-pregnene-3 ,20-d ione
REACTION
utilization
util ization
1
Δ
utilization
util ization
Δ4
1
Δ
1
Δ ; enol. 1
Δ
Δ 1
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
Δ 1
1
Δ
1
Δ
1
Δ
1
Δ 1
Δ
R E F .
S-793c
S-793c
T-1005
S-793c
S-793c
S-939
S-939
3-37
ß - 3 7
ß - 3 7
ß - 3 7
B-37
ß - 3 7
ß - 3 7
ß - 3 7
B-37
ß - 3 7
ß - 3 7
A-7
ß - 3 7
H-401
502
TABLE I I I
Transformat ions by Genus: NÛCARDIA
SPECIES
opaca
paraffinae
polychromogenes
r e s t r i c t u s
SOURCE
ATCC-4276
SQ (SC-2812) (WC-560)
NG
NG
AY
NCTC-6846
Sp-WISC
SUBSTRATE
14a, 17a, 21 - t r ihydroxy-4 -p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
4 ,16-pregnad iene-3 ,20-d ione
17a,21 -dihydroxy-4,9(11) -pr egnadiene-3 ,20- t r ione
17a ,21-d ihydroxy-4 ,14-pr egnadiene -3 ,20 -dione
17a -hydroxy-21-me thy l -4 ,9 ( l l ) -pr egnadiene -3 ,20 -dione
9a - f luo ro - l l / 3 ,17a ,21 - t r i hy -droxy-4-pregnene-3 ,20-d ione
5-cholesten-3/3-ol (sole carbon source)
24j3-methyl-5 ,7-22-choles ta-trien-3/3-ol (sole carbon source)
5-cholesten-3j3-ol (sole carbon source)
24i3-methyl-5 ,7-22-choles ta-t r i e n - 3/3-ol (sole carbon source)
19-hydroxy-4, 7 -andros tad iene-3,17-dione
19-methoxy-4, 7 -andros tad iene-3,17-dione
5-cholesten-3j3-ol
1 7j3 -hy dr oxy - A -_nor - 3 -andr osten -2-one
9a -hyd roxy-4 -and ros t ene -3 ,17 -dione (enzyme preparat ion)
17/3-hydroxy-5-androsten-3-one cycloethyleneketal
3 ,4-dihydroxy - 9 ,10 ^s_eço-1,3, 5(10)-andros tene-9 ,17-dione (cell free extract)
4 -pregnene-3 ,20-d ione
REACTION
Δ1
Δ1
Δ 1
Δ1
Δ1
Δ1
utilization
utilization
utilization
utilization
Δ1; r ev . aldol; enol.
Δ1; r ev . aldol; enol.
util ization
9a-OH·, 17/3-OH-» 1 7 - C = 0
Δ1; r ev . aldol; enol.
1 7 β - Ο Η -1 7 - C = 0
degradation [A,B1
Δ 1
9a-OH
R E F .
B-37
B-37
B-37
B-37
H-391
T-1005
S-793c
S-793c
S-793c
S-793c
B-38
B-38
M-595
S-885
S-885
S-885
S-896
S-885
S-885
TABLE I I I
503
T r a n s f o r m a t i o n s by Genus: NOCARDIA
SPECIES
restrictus
1 *
1 *
SOURCE
Sp-WISC
SQ
SQ(SC-2914 SC-2915 SC-2917 SC-2919)
WC(545)
SUBSTRATE
4-pregnene-3 ,20-d ione (with KCN)
9 a - f l u o r o - l l ß , 17α, 2 1 - t r i -hydroxy-4 -p regnene -3 ,20 -dione
3/3, 5/3,14j3-trihydroxy-19-oxo-20(22)-cardenolide
14/3-hydroxy-3,19-dioxo-4,20 (22) -cardadienolide
14/3-hydroxy -3 -keto-19 -nor -4 ,20(22)-cardadienol ide
17/3-hydroxy-4-estren-3-one
17ß-hydroxy-4-andros ten-3-one
17a ,21-d ihydroxy-4-pregnene-3,20-dione
l l j 3 ,17a ,21 - t r ihydroxy-4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
9a- f luoro- l l /3 ,17o ,21- t r ihydroxy 4 -pregnene-3 ,20-d ione
5-cholesten-3/3-ol
17j3-hydroxy-A-nor-3-androsten-2-one
17j3-hydroxy-17a-methyl-A-nor-3 -andros ten-2 -one
A, 19 -b i sno r -3 -and ros t ene -2 .17 -dione
REACTION
9a -OH; 17j3-Ac-+ 1 7 - C = 0
Δ1
3 /3 -OH-3 - C = 0 ; 50-ΟΗ-+Δ4
3/3-OH -3 - C - O ; δ β - Ο Η - Δ ^ Δ 1 ; 1 0 ß - H C = O ^ 10/3-H; enol.
Δ1; 10/3-HC-O -» 10/3-H; enol.
Δ1; enol.
Δ1; enol.
Δ 1
Δ1
Δ1
Δ1
Δ1
Δ 5 - Δ 4 ; 3 j3-OH^ 3 - C = 0
9a-OH; 17 /3-OH-1 7 - C = 0
9a-OH
9a-OH
R E F .
S-885
S-885
K-481
K-481
K-481
K-481
S-889
S-889
S-889
S-889
T-1005
T-1005
T-1005
W-1080
W-1080
W-1080
504
TABLE I I I
T r a n s f o r m a t i o n s by Genus: NOCARDIA
SPECIES
r e s t r ictus
SOURCE
WC(545)
SUBSTRATE
17/3-hydroxy-4-androsten-3-one
4 -andros tene-3 ,17-d ione (cell free extract-Ref . S-883)
9a -hydroxy-4 -and ros t ene -3 ,17 -dione (cel l -free extract)
19 -hydroxy-4 -andros tene -3 ,17-dione
4 -andros tene -3 ,17 -dione
A - n o r - 3 - pr egnene -2 ,20 -dione
4 -pregnene-3 ,20-d ione (cell free ex t rac t - Ref. S-883)
REACTION
Δ 1
9α-ΟΗ; Δ1; rev . aldol; eno l . ; 17ß-OH - 1 7 - C = 0
9α-ΟΗ; Δ1; r ev . aldol; eno l . ; 9 - C = 0 -9/3-OH 17/3-OH-1 7 - C = 0
9α-ΟΗ; Δ 1
r ev . aldol; eno l . ; 9 - C = 0 - 9 a - O H 17/3-OH-1 7 - C = 0
1 7 - C = 0 -17/3-OH; 9a-OH; Δ1; r ev . aldol; enol. ; 9 - C = 0 - 9 / 3 - O H
17/3-OH-1 7 - C = 0 degradation; [A ,ß ]
Δ 1
9α-OH
9α-OH; Δ1; r ev . aldol; enol.
Δ1; r ev . aldol; enol.
Δ ; r ev . aldol; enol.
degradation; [A,B]
9a-OH
Δ1
R E F .
S-883
W-1063
W-1063
W-1063
W-1063
W-1063
S-883; S-884; S-894
S-884; S-894
S-884; S-894; S-895
S-884; S-894
S-884; S-894
S-895
W-1079
S-883; T-1005
TABLE I I I
505
T r a n s f o r m a t i o n s by G e n u s : NOCARDIA
SPECIES
r e s t r i c t u s
*
1 *
r u b r a * (Mycobacterium rhodo-ch rous - J . ßac t . 73 :15 , 1957) ~~ salmonicolor
1 *
1 spec ies
SOURCE
WC(545)
SQ(SC-2823) (vVC-546)
NG
NG
SQ(SC-2750) (WC-647)
ATCC-13259
ATCC-13934
SUBSTRATE
4-pregnene-3 ,20-d ione (use of inhibitor s-Ref. S-898)
17α, 21 -dihydroxy -4 -pr egnene -3,20-dione (cel l -free extract)
l l / 3 ,17a ,21 - t r i hyd roxy-4 -pregnene-3 ,20-d ione (cel i -free extract)
9a - f luo ro - l l / 3 ,17a ,21 - t r i hy -d roxy-4-p regnene-3 ,20-d ione (cel l -free extract -Ref . S-883)
9a - f l uo ro - l l / 3 ,16α ,17α ,21 -t e t r ahydroxy-4 -p regnene -3,20-dione (cel l - f ree extract)
17a ,21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione (cel l - f ree extract)
5-cholesten-3j3-ol
9 a - f l u o r o - l l / 3 , 1 7 a , 2 1 - t r i -hydroxy-4 -p regnene -3 ,20 -dione
5-cholesten-3/3-ol (sole carbon source)
24/3-methyl -5 ,7 ,22-choles ta -tr ien-3/3-ol (sole carbon source)
9a - f l uo ro - l l j 3 , 17a ,21 - t r i -hydroxy-4 -p regnene -3 ,20 -dione
4 -andr ostene -3 ,17 -dione
4 , 9 ( l l ) - a n d r o s t a d i e n e - 3 , 1 7 - d i o n e
17a-(21-carboxyethyl)-17ß-hydroxy-4-andros ten-3-one spirolactone
REACTION
9a-OH
17/3-Ac-> 1 7 - C = 0
Δ1
9a-OH
Δ 1
1
Δ
Δ 1
1
Δ
Δ5->Δ4; 3/3-OH->3-C=0
Δ 1
util ization
utilization
Δ 1
9α-ΟΗ; Δ1; r ev . aldol; enolo
9α, 11α-oxide
9α-OH
R E F .
P -740 ; S-897; S-898
S-898
S-883
P-740
S-883
S-883; S-884; S-894; T-1005
S-883; T-1005
S-883
T-1005
T-1005
S-793c
S-793c
T-1005
D-171
S-886
D-173
506
TABLE I I I
T ransformat ions by Genus: NOCARDIA
SPECIES SOURCE SUBSTRATE REACTION R E F .
species ATCC-13934
ATCC-14558
ATCC-14559
Searle (A-20-10)
NG
4-pregnene-3 ,20-d ione
17a-hydroxy-4-pregnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
17a ,21 -d ihyd roxy -4 ,9 ( l l ) -pregnadiene-3 ,20-d ione
12a-aza - 3/3 - hydr oxy - C - homo-5a-pregnane-12 ,20-d ione
12a-aza-3/3 ,17a-dihydroxy-C-homo_-5a-pr e gnane -12,2 0-dione
4 -andros tene-3 ,17-d ione
21-hydroxy-4 -p regnene-3 ,20-dione
3a, 7a, 12a-tr ihydroxy-5/3-choianic acid
5-cholesten-3/3-ol (sole carbon source - Ref. S-793c)
9a-OH;17ß-Ac - 1 7 - C = 0
9a-OH
D-172
D-172
9a-OH; 17/3-Ac -*17.β-ΟΗ
17/3-Ac-17-c=o 9a-OH
9a-OH
o ( l l )
Δ v - 9 a , 11a-oxide
3/3-OH-*3-C=0; Δ1»4 (5a-H)
3 /3 -OAc-3 - C = 0 ; Δ 1 ' 4
9a-OH
9a-OH; Δ*; r ev . aldol; enol.
9a-OH
degradation
Δ 5 -Δ 4 ;3 /3-ΟΗ - 3 - C = 0
3/3-OH->3-C=0; Δ 5
Γ Δ 4 ; 17/3-(2 -isooctyl) —► 17-C = 0
5 4 !
Δ 5 - Δ 4 ; Δ ;
D-172
D-172
D-173
D-173
S-886
M-563
M-563
D-170
S-796
H-330
L-501 ; S-793c
W - l l l l
W - l l l l 3/3-OH->3-C=0; 17/3-(21-isoocty0| - 1 7 - C = 0
3/3-OH—3-C-0; Δ 5 -Δ 4 ;17 /3 - (2 χ -isooctyl)-»17/3-(2 -propionic acid)
W - l l l l
507
T r a n s f o r m a t i o n s by Genus:
TABLE I I I
NOCARDIA OÏDIUM
OMPHALIA OOSPORA
TAXONOMY
(Imperf. - Moniliales) (ßas id io . - Agar icales) (Imperf. - Moniliales)
SPECIES SOURCE SUBSTRATE REACTION
species
OÏDIUM
species
OMPHALIA
t ra lucida (in mixed cul ture with| T r i choderma v i r i d e -NRRL-2473[17a-OH] and Wojnowicia graminis - NRRL-2472 [21-OH])
OOSPORA
aurant i i
lact is
NG
SQ
NRRL
MCC
TNAES
UC
5-cholesten-3/3-ol (sole carbon source)
24/3-methyl-5,7,22-cholesta-trien-3ß-ol (sole carbon source)
plant saponins
4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
not given
3j3-OH->3-C = 0 ; Δ 5 - Δ 4 ; Δ^,ΙΊβ-(2x-isooctyI)-> 17/3-(21-prop-ionic acid)
utilization
decomposit ion
A 1>4
9a -OH
11/3-OH
oxidation
REF.
W - l l l l
S-793c
S-794
S-887; S-888
S-887; S-888
S-887; S-888; S-897
S-897
K-478
M-566
S-849
M-601; M-636
digitonin
5a-pregnane-3,20-dione
5/3-pr egnane -3,20 -dione
4-pregnene-3,20-dione
(use of inhibitors)
1
Δ
1
Δ
508
TABLE I I I
T r a n s f o r m a t i o n s by Genus : OPHIOBOLUS
TAXONOMY
(Asco. - Sphaeriales)
SPECIES SOURCE SUBSTRATE REACTION R E F .
graminis
herpotr ichus
( in mixed cul ture with one of the following: Curvular ia b lakes -leanna [110-OH; 1 1 -C=0] - Curvular ia brachyospora [11/3-OH] - Curvular ia l u n a t a [ l l ß - O H ] -Rhizopus n igr icans [11a-OH])
NARI
C
17a ,21-d ihydroxy-4-pregnene-3,20-dione
d, l - 1 9 - n o r - 4 - p r e g n e n e - 3 , 20-dione
4 -p regnene-3 , 20-dione
d , l - 4 - p r e g n e n e - 3 , 20-dione
17a-hydroxy-4-pregnene-3 ,20-dione
d , l -9a - f luo ro - l l / 3 -hydroxy-4 -pregnene-3 ,20-d ione
d, 1-11/3, 18/3-dihydroxy-4-preg-nene-3 ,20-d ione
4 -p regnene -3 ,11 ,20 - t r i one
d , l - i l / 3 -hydroxy-3 ,20 -d ike to -4 -p regnen-18-o ic acid (18-11) lactone
11/3,16a -dihydroxy -3 ,20 -diketo-4-pregnen-18-o ic acid (18-11) lactone
d , l - l l / 3 -hydroxy-3 ,20 -d ike to -4-pregnen-18-a l (18— 11) hemiaceta l
1,4 -pregnadiene -3 ,20-dione
11 /3 ,17a-d ihydroxy- l ,4 -preg-nadiene -3 ,20-dione
17a-hydroxy-1 ,4-pregnadiene -3 ,11 ,20 - t r ione
4 -pregnene-3 ,20-d ione
11a-OH
d , l -> d-21-OH
S-849
W-1102 + 1
21-OH
d , l - d-21-OH + 1
21-OH
d , l - d - 2 1 - O H + 1
d , l - d - 2 1 - O H + 1
21-OH
M-584; W-1101
W-1102
M-584; W-1101
W-1102
W-1102
M-584; W-1101
d , l - d -+ 1
d , l -
21
d-21-OH +
21-OH
d , l - d + 1
21-OH
21-OH
21-OH
21-OH
-21
OH
1
-OH
W-1101; W-1102
V-1055
W-1091
W-1102
W-1101
W-1101
W-1101
W-1106
TABLE I I I
509
T r a n s f o r m a t i o n s by Genus : OPHIOBOLUS
SPECIES
herpotr ichus (in mixed cul ture with
Trichothecium roseum |17a-OH|)
(in mixed cul ture with one of the following: Calonectr ia decora lA^-Curvu la r i a brachyspora [11/3-OH | -Tr ichothecium roseum [17a-OH])
(in mixed cul ture with Trichothecium ro seum 117a-OH]
Calonectr ia decora ΙΑΊ)
(in mixed cul ture with 1 Calonectr ia decora
lA^-Tr ico thec ium roseum [17a-OH])
(in mixed cul ture with Cunninghamella blakesleeana [11/3-OH] -Tr ichothecium roseum 117a-OH])
(in mixed cul ture with Trichothecium ro seum [17a-OH])
(in mixed cul ture with Trichothecium ro seum [17a-OH])
(in mixed cul ture with Curvular ia b rachy-spora [11/3-OH])
SOURCE
C
PIRI .
SCH
SUBSTRATE
4-pregnene-3 ,20-d ione
11/3 -hydroxy -4 - pr egnene - 3 , 2 0 -dione
4 - p r e g n e n e - 3 , 1 1 , 20- t r ione
1,4 -pr egnadiene -3 ,20-d ione
11/3-hydroxy-1,4-pregnadiene -3,20-dione
1,4 -pregnadiene - 3 , 1 1 , 2 0 - t r i o n e
4 - p r e g n e n e - 3 , 1 8 , 20- t r ione
4 -pregnene-3 ,20-d ione
3/3-hydroxy-5,16-pregnadien-20-one
11/3,17a -dihydr oxy -1 ,4 -pr egna -d iene-3 ,20-d ione
17a-hydroxy-1 ,4-pregnadiene -3 , 1 1 , 20- t r ione
11a -hyd roxy-1 ,4 ,16 -p regna -t r i ene -3 ,20 -d ione
l l / 3 - h y d r o x y - l , 4 , 1 6 - p r e g n a -t r i e n e - 3 , 20-dione
REACTION
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
Δ 4 - 5 α - Η
21-OH
21-OH
21-OH
21-OH
21-OH
R E F .
W-1106
W-1107
W-1106; W-1107
W-1107
W-1106; W-1107
W-1106
W-1106
W-1106
W-1106
W-1081
W-1081
H-388; O-700
H-388; O-700
H-388; O-700
H-388; O-700
H-388; O-700
510
TABLE I I I
Transformat ions by Genus: OPHIOBOLUS
SPECIES
herpotr ichus
he teros t rophus
SOURCE
uc
WFEB
C
NIHJ
S
SUBSTRATE
4 ,14-pregnad iene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
3j3-hydroxy-5-androsten-17-one
4 -andros tene-3 ,17-d ione
3/3-hydroxy-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
l i a , 21-dihydroxy-4-pregnene -3,20-dione
11/3,21-dihydroxy-4-pregnene -3,20-dione
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
1 l a , 1 la, 21 - t r ihydr oxy -4 -p regnene-3 ,20-d ione
11/3,17a, 21 - t r ihydr oxy - 4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r ione
17a-hydroxy-3 ,20-d ike to -4-p regnen-18-a i
l l ß , 21 -dihydroxy -3 ,20-d ike to -4 -p regnen-18-a l (18-+11) hemiaceta l
17a, 21 -dihydroxy-4 -pregnene -3,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
11/3,21a-dihydroxy-4-pregnene -3,20-dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
l l / 3 ,17a ,21 - t r i hyd roxy-4 -pregnene-3 ,20-d ione
REACTION
21-OH
21-OH (0218)
Δ1
Δ 1
Δ1
Δ1
Δ1
Δ1
Δ1
Δ1
1
Δ
Δ1
Δ1
Δ 1
Δ1
1
Δ
1
Δ
Δ1
Δ1
R E F .
M-576; M-577
H-374
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
S-849
S-849; S-857
S-849; S-857
S-849; S-857
S-849; S-857
TABLE I I I
T ransformat ions by Genus: OPHIOBOLUS
SPECIES
heteros t rophus
miyabeanus
sat ivus
SOURCE
S
c
FRI
S
NARI
SUBSTRATE
17a, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r ione
3ß-hydroxy-5-andros ten -17-one
4 -andros tene -3 ,17 -dione
3ß-hydroxy-5-pregnen-20-one
3/3 ,21-dihydroxy-5-pregnen-20-one
4 -p regnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
1 l ö , 21 -dihydroxy -4 -pregnene -3,20-dione
11/3,21-dihydroxy-4-pregnene -3,20-dione
17o, 21 -dihydroxy-4-pregnene -3,20-dione
1 l a , 1 la, 21 - t r ihydr oxy -4 -p regnene-3 ,20-d ione
l l / 3 , 17a ,21 - t r i hyd roxy -4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r ione
17a-hydroxy-3 ,20-d ike to -4-p regnen-18-a l
l l /3 ,21-d ihydroxy-3 ,20-d ike to -4 -p regnen-18-a l (18-^11) hemiaceta l
17a, 21-d ihydroxy-4-pregnene-3,20-dione
4 -p regnene-3 ,20-d ione
17a-hydroxy-4-pr e g n e n e - 3 , 2 0 -dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21 -d ihydroxy-4-pregnene-3, 20-dione
REACTION
Δ 1
Δ1
1
Δ
Δ1
Δ1
Δ1
Δ1
Δ1
Δ1
Δ1
Δ1
Δ1
Δ1
Δ1
Δ 1
l i a - O H
Δ1
6ß-OH
R E F .
S-849; S-857
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
W-1105
S-849
S-859
S-859
S-849; S-859
S-849
511
512
T r a n s f o r m a t i o n s by G e n u s :
TABLE I I I
OPKIOBOLUS OPHIOSTOMA
PAECILOMYCES PANAEOLUS
TAXONOMY
(Asco. -Sphaeriales) (Imperf. - Moniliales) (Basidio0 - Agaricales)
! ! SPECIES
species
OPHIOSTOMA
catanianum
PAECILOMYCES
species
vari toi
PANAEOLUS
papilionaceus
SOURCE
C
NG
NG (Sandoz-
904)
NRRL
FRI
AL (G-60)
SUBSTRATE
4-pregnene-3 ,20-d ione
21-hydroxy-4-p regnene-3 ,20-dione
1 Iß , 21 -dihydr oxy -4 -pregnene -3,20-dione
17flf, 21-d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3 ,11 ,20- t r ione
5-cholesten-3/3-ol (sole carbon source)
24/3-methyl -5 ,7 ,22-choles ta-trien-3/3-ol (sole carbon source)
3/3, 6/3, 8/3,14/3-tetrahydroxy-4, 20,22 -bufatrienolide 6-acetate 3-glucoside
3/3,14/3-dihydroxy-5/3-20(22)-cardenol ide-3- |g lucosy l -digitoxosyl-digitoxosyl-digitoxosidel
Digilanid A
plant saponins
17a, 21 -dihydroxy-4 -pregnene -3,20-dione
4-pregnene-3 ,20-d ione
REACTION
Δ ^ Π β - Α ΰ -17-C = 0
1
Δ
1
Δ
Δ1
1
Δ
utilization
utilization
3/3|lVgluco-s ide | -3/3-OH
glucosyl-digitoxosyl-digitoxosyl —» digitoxosyl-digitoxosyl-digitoxoside
select ive cleav-age of glucose from sugar chain
-
—
oxidation -products not identified
R E F .
V-1053
V-1053
V-1053
V-1053
V-1053
S-793c
S-793c
S-936a
S-936a
S-936a
K-478
S-849
S-825
513
T r a n s f o r m a t i o n s by G e n u s :
TABLE I I I
PANELLUS PARASITELLA
PARENDOMYCES PAXILLUS
PELLICULARIA
TAXONOMY
(ßasidiOo - Agaricales) (Phyco. - Mucorales) (Imperf. - Moniliales) (Basidio. - Agaricales) (3as id io . - Agaricales)
SPECIES
PANELLUS
stypticus (stipticus)
PARASITELLA
simplex
PARENDOMYCES
as té ro ïdes
PAXILLUS
involutus
vernal is
PELLICULARIA (see Corticium)
filamentosa f. s. t ims i i
f. s. sasaki i
f. s. solani
f. s. mic rosc le ro t i a
NOTE: f. s. = forma 1 sec iaus
SOURCE
AL (C-224)
FRI
FRI
AL (H-19)
AL (H-25)
IFO (6259)
IFO(6298)
SUBSTRATE
4-pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3, 20-dione
17a, 21-dihydroxy-4-pregnene -3, 20-dione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4-pregnene -3, 20-dione
9a -hyd roxy -4 -and ros t ene -3 ,17 -dione
1Iß - hyd roxy-4 -and ros t ene -3 ,17 -dione
14a -hydroxy-4 -andros t ene -3 ,17 -dione
REACTION
oxidation -products not identified
oxidation -products not identified
oxidation -products not identified
6/i-OH; l l a - O H
6/J-OH; l l a - O H ; 11/i-OH; 19-OK
Δ1; 6/3-OH; l l a - O H
6/i-OH; 14a-OH
l l j 3 - O H - l l - C = O; 14a-OH
l l a - O H ; 11/3-OH
R E F .
S-825
S-849
S-849
S-825
S-825
T-957
T-957
T-957
T-955
T-955
T-955
514
TABLE I I I
Transformat ions by Genus: PELLICULARIA PENICILLIUM
TAXONOMY
(Imperf. - Moniliales)
SPECIES
filamentosa f. s. mic rosc le ro t i a
PENICILLIUM
aculeatum
adametzi
*
NOTE: f. s. = forma sec iaus
SOURCE
IFO(6298)
CZAS
ATCC-10407
CZAS
SUBSTRATE
15a-hydroxy-4-andros tene -3 ,17-dione
4 - a n d r o s t e n e - 3 , 1 1 , 1 7 - t r i o n e
1,4 -androstadiene -3 ,17 -dione
l l / 3 -hyd roxy- l , 4 - and ros t ad i ene -3,17-dione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
17a ,20a ,21 - t r i hydroxy-4 -pregnen-3-one
l l / 3 ,17a ,21 - t r ihydroxy-4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
5/3-pregnane-3,20-dione
4-pregnene-3 ,20-d ione
17a-hydroxy-4-pregnene-3 ,20-dione
21-hydroxy-4-p regnene-3 ,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
4 ,16 -p regnad iene -3 , 20-dione
4 -pregnene-3 ,20-d ione
REACTION
11/3-OH; 11-C = 0 (via 11/3-OH)
14a-OH
14a-OH; 11/3-OH; 11-C = 0 (via 11/3-OH)
14a-OH; 11/3-OH-n-c=o l l a - O H ; 11/3-OH; 19-OH
11/3-OH; 19-OH
2 0 - C = O -20/3-OH
oxidation -product not identified
oxidation -product not identified
oxidation -product not identified
oxidation -product not identified
oxidation -product not identified
oxidation -product not identified
17/3-Ac-> 17a-oxa-17 -C=0
R E F .
T-955
T-955
T-955
T-955
T-957
T-953; T-954
T-953; T-954
C-99
M-602
M-602
M-602
M-602
M-602
M-602
C-99
TABLE I I I
515
T r a n s f o r m a t i o n s by G e n u s : PENICILLIUM
SPECIES
adametzi (in mixed cul ture with Tr ichoderma lignorum [17a-OH) and Wojnowicia graminis [21-OH|)
albidum *
*
*
1 *
aspe rum *
a t ramentosum *
1 *
aurantio - violaceum
auran t io -v i rens
avelianeum
biforme
brefeldianum
brevi -compactum
SOURCE
MCC
NRRL
UÇ
ASRI
CZAA
CZAS
FCUTS
MCC
CZAS
MCC
ASRI
CZAS
MCC
MCC
MCC
CZAS
ASRI
CZAS
FCUTS
MCC
MCC
ATCC-9056
SUBSTRATE
4-pregnene 3,20-dione
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
REACTION
11a-OH
-
-
-
17j3-Ac-17a-oxa-17-C = 0
17/3-Ac-17a-oxa-17-C = 0
17/3-Ac->17a-oxa-17-C = 0
17/3-Ac-17a-o x a - 1 7 - C = 0
17/3-Ac—17a-o x a - 1 7 - C = 0
none at C - l l
17/3-Ac— 17a-oxa-17-C = 0
none at C - l l
l l a - O H
l l a - O H
none at C - l l
none at C - l l
none at C - l l
-
—
-
-
none at C - l l
none at C - l l
oxidation -products not identified
R E F .
M-566
M-587
M-587
M-587
P-726
C-99
C-99
C-99
C-99
D-190
C-99
D-190
C-99
C-99
D-190
D-190
D-190
C-99
C-99
C-99
C-99
D-190
D-190
M-602
516
TABLE I I I
Transformations by Genus: PÉNICILLIUM
SPECIES
br evi - compactum
camember t i
canescens
*
*
*
casei
caseicolum
char les i i
SOURCE
ATCC-9056
CZAS
MCC
CZAS
MCC
ATCC-10419
ASRI
CZAS
MCC
ASRI
FCUTS
MCC
ASRI
CZAA
CZAS
FCUTS
UC
SUBSTRATE
4-pregnene-3 ,20-d ione
(revision of s t ruc tu re -20a to 20ß - Ref. S-832)
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -p regnene -3 , 20-dione
4-pregnene-3 ,20-d ione
5/3-pregnane-3,20-dione
4-pregnene-3 ,20-d ione
21-hydroxy-4-p regnene-3 ,20-dione aceta te
21-hydroxy-4-p regnene-3 ,20-dione aceta te (revision of s t ruc tu re -20a to 20/3 - Ref. S-832)
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
21-hydroxy-4-p regnene-3 ,20-dione aceta te
(revision of s t ruc tu re -20a to 20/3-Ref. S-832)
REACTION
17/3-Ac^ 1 7 - C = 0
2 0 - C = O -20/3-OH
—
none at C-11
—
none at C-11
170-Ac — 1 7 - C = 0
oxidation -products not identified
17ß-(20-C=O-21-OAc) -1 7 - C = 0
20-C=O -* 20/3-OH 21-OAc -21-OH
17 /3 -Ac^ l7a -oxa-17-C = 0
17/3-Ac^l7a-o x a - 1 7 - C = 0
none at C-11
-
-
none at C-11
-
-
-
-
17/3-(20-C=O -21-OAc) -> 1 7 - C = 0
20-C=O-> 20j3-OH; 21-OAc -> 21-OH
R E F .
M-637
M-637
C-99
D-190
C-99
D-190
M-637
M-602
M-637
M-637
Çf_99
C-99
D-190
C-99
C-99
D-190
C-99
C-99
C-99
C-99
M-637
M-637
TABLE I I I
Transformat ions by Genus: PÉNICILLIUM
517
SPECIES
chermes inum
chrysogenum *
*
*
*
*
c i t r eo -v i r ide *
SOURCE
CZAS
FCUTS
MCC
ASRI
AY
CZAS
IPB
MCC
MCC(MF-2133)
NRRL
SQ
WISC(48-701)
WISC (49-133)
CZAS
MCC
SUBSTRATE
4-pregnene-3 ,2 0-dione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione (use of conidia)
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
Diosgenin (dioscorea tuber pulp)
plant saponins
3j3-hydroxy -5 -pregnen-20-one
21-hydroxy-4 -p regnene-3 ,20-dione
4 -andros tene-3 ,17-d ione
17a -oxa-D-homo-4-andros tene -3,17-dione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
REACTION
—
-
none at C-11
17/3-Ac-17a-o x a - 1 7 - C = 0
17α-ΟΗ-17β-(20-C=O-21-OH) -> 17-C = 0
17/3-Ac-17a-o x a - 1 7 - C = 0
17/3-Ac-1 7 - C = 0
none at C-11
3/3-glycoside (Dioscin) —* 3/3-ΟΗ·3β-ΟΗ - > 3 - C = 0 ; Δ 5 - Δ 4
hydrolysis of gly cos ides to aglycones (sapogenins)
Δ 5 - Δ 4 ; 3/3-ΟΗ - 3 - C = 0
11/3-OH
no tes tol ic acid
17a-oxa-17-C = 0 - > 1 3 , 1 7 -seco-13ö-OH-16-COOH
17j3-Ac—17a-o x a - 1 7 - C = 0
17/3-Ac—13,17-seco-13a-OH-16-COOH
17j3-Ac-17a-o x a - 1 7 - C = 0
none at C-11
R E F .
C-99
C-99
D-190
C-99
V-1048
C-99
C-102
D-190
R-781
K-478·, K-479
P-710
H-328
H-398
H-398
F-270·, F-284
H-398
C-99
D-190
518
TABLE I I I
Transformat ions by Genus: P É N I C I L L I U M
SPECIES
ci t r inum *
*
*
*
*
*
*
SOURCE
ASRI
ATCC-8506
ATCC-10105
CZAS
FRI
I P ß (THOM)
MCC
S
SUBSTRATE
4-pregnene-3 ,20-d ione
A-nor-17j3-hydroxy-3-androsten-2-one
4 -andros tene-3 ,17-d ione
17a-oxa-D-homo-4-andros tene -3,17-dione
4 -pregnene-3 ,20-d ione
6/3-hydroxy-4-pregnene-3,20-dione
4-pregnene-3 ,20-d ione
17«, 21-d ihydroxy-4-pregnene-3,20-dione
4 -andr ostene -3 ,17 -dione
4-pregnene-3 ,20-d ione
1 lûf-hydroxy-4-pregnene-3, 20-dione
17a-hydroxy-4-pregnene-3 ,20-dione
4 -p regnene -3 ,11 ,20 - t r i one
4 -pregnene-3 ,20-d ione
4 -androstene -3 ,17 -dione
4-pregnene-3 ,20-d ione
REACTION
17/3-Ac-^ 17/3-OH
17/3-OH—17a-o x a - 1 7 - C = 0
no tes tol ic acid
17a-oxa-17-C= 0 —13,17-seco-13ö-OH-16-COOH
1 7 ß - A c - 1 7 a -o x a - 1 7 - C = 0
17/3-Ac->13,17-seco-13a-OH-16-COOH
oxidation -products not identified
17/3-Ac -» 1 7 - C = 0
1 7 0 - A c -17/3-OH
-
17-C = 0 -17/3-OH
17/3-Ac — 17/3-OH
17/3-Ac -1 7 - C = 0
17/3-Ac — 17/3-OH
17a-OH-17/3-Ac-17/3-OH
17/3-Ac -17/3-OH
none at C - l l
1 7 - C = 0 - 1 7 a -o x a - 1 7 - C = 0
17/3-Ac— 17a-o x a - 1 7 - C = 0
R E F .
C-99
L-500
H-398
H-398
F-270
H-398
M-602
M-637
C-99
S-849
H-336
H-336
C-102
H-336
H-336
H-336
D-190
S-846
S-846
4-pregnene-3,20-dione
TABLE I I I
519
T r a n s f o r m a t i o n s by G e n u s : PENICILLIUM
SPECIES
ci t r inum
claviforme
clavigerum
commune *
1 *
corylophilum *
1 *
I corymbiferum
SOURCE
S
SQ
CZAA
CZAS
RIDPI
ASRI
CZAS
ASRI
CZAS
ASRI
CZAS
MCC
ASRI
SUBSTRATE
17a-hydroxy-4-p regnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
11/3,21-dihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-dione
1 7a , 21 -dihydr oxy -4 -pr egnene -3 ,11 ,20- t r ione
A-nor-17/3-hydroxy-3 -andr osten -2-one
A-nor -3 -p regnene -2 ,20 -d ione
4 -p regnene -3 ,11 ,20 - t r i one
9 a - f l u o r o - 4 - p r e g n e n e - 3 , 1 1 , 2 0 -t r ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
REACTION
17a-OH-17/3-Ac —17a-oxa-1 7 - C = 0
17/3-(20-C=O-21-OK) -»17a-oxa-17-C = 0
-
20-C = O -20/3-OH
-
-
17/3-OH — 17a-oxa-17-C = 0
17/3-Ac— 17a-o x a - 1 7 - C = 0
17/3-Ac—17a-o x a - 1 7 - C = 0
1 7 ß - A c - 1 7 a -o x a - 1 7 - C - O
-
-
-
-
-
17/3-Ac-17a-o x a - 1 7 - C = 0
17/3-Ac-17a-oxa-17-C = 0
17/3-Ac-17/3-OH
17/3-Ac-17/3-OH
11a-OH
R E F .
S-846
S-846
S-846
S-846
S-846
S-846
L-502
L-502
L-492
L-492
C-99
C-99
C-99
C-99
C-99
C-99
C-99
C-99
C-99
D-190
C-99
520
TABLE I I I
T r a n s f o r m a t i o n s by Genus: PENICILLIUM
SPECIES
corymbiferum
crus tosum
cyaneofulvum *
*
cyaneum
cyclopium
(Westling) *
daleae
*
decumbens *
*
*
*
SOURCE
CZAS
MCC
CZAS
MCC
ASRI
CZAS
MCC
MCC
CZAS
MCC
NG
N R R L -942, 1888, 1889, ERRL-1292
MCC
RIDPI
ASRI
CZAS
FCUTS
IPB
SUBSTRATE
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -p regnene-3 i 20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
plant sap on in s
plant saponins
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -andros tene -3 ,17 -dione
4 -pregnene-3 ,20-d ione
1 l a -hyd roxy -4 -p regnene -3 ,20 -dione
1 l a -hydroxy-4 -p regnene -3 ,20 -dione
4 -p regnene -3 ,11 ,20 - t r i one
REACTION
_
none a t C-11
-
none at C-11
17/3-Ac—17a-o x a - 1 7 - C = 0
17/3-Ac-*17a-o x a - 1 7 - C = 0
none at C-11
none at C-11
-
none at C-11
hydrolysis of glycosides to aglycones (sapogenin)
hydrolysis of glycosides to aglycones (sapogenin)
none at C-11
17/3-Ac-» 17a-o x a - 1 7 - C = 0
17/3-Ac—17a-o x a - 1 7 - C = 0
17/3-Ac-* 17a-o x a - 1 7 - C = 0
17/3-Ac-» 17a-o x a - 1 7 - C = 0
1 7 - C = 0 -> 17/3-OH
17/3-Ac-» 17/3-OH
17/3-Ac-»17j3-OH
17a -OH -17/3 -Ac -»17/3-OH
17/3-Ac-»17/3-OH
R E F .
C-99
D-190
C-99
D-190
C-99
C-99
D-190
D-190
C-99
D-190
K-479
K-478
D-190
C-99
C-99
C-99
C-99
H-336
H-332·, H-336
H-336
H-336
H-336
T r a n s f o r m a t i o n s by G e n u s :
SPECIES
decumbens
digitatum
diversum *
duponti
egyptaceum *
*
*
*
ehrl ichi i
expansum
SOURCE
MCC
CZAS
MCC
NG (Sandoz-872)
CZAS
FCUTS
MCC
ASRI
CZAS
FCUTS
SSSR
MCC
ASRI
ATCC-7861
CZAA
CZAS
FCUTS
MCC
NRRL
SUBSTRATE
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
3/3, 6/3, 8/3,14/3-tetrahydroxy-4, 20,22-bufatr ienol ide 6-aceta te 3-glucoside
3ß, 14/3-dihydroxy-5j3-20(22)-cardenolide 3[glucosyl-digitoxosy I -digitoxosy 1 -digitoxoside]
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
REACTION
none at C - l l
-
none at C - l l
3 / 3 - [ l V g l u c o -s ide l -3 /3 -OH
glucosyl-digitoxosyl-digitoxosyl -digitoxoside -* digitoxosy 1-digitoxosyl-digitoxoside
15/3-OH
15/3-OH
none at C - l l
17/3 - A c - 17a-o x a - 1 7 - C = 0
17/3 - A c - 17a-o x a - 1 7 - C = 0
17/3-Ac->17a-o x a - 1 7 - C = 0
17/3-Ac-17a-o x a - 1 7 - C = 0
none at C - l l
—
oxidation -products not identified
17/3-Ac -17-C = 0
-
-
-
none at C - l l
-
-
-
REF.
D-190
C-99
D-190
S-936a
S-936a
C-99
C-99
D-190
C-99
C-99
C-99
C-99
D-190
C-99
M-602
M-637
C-99
C-99
C-99
D-190
M-587
M-587
M-587
TABLE I I I
PENICILLIUM
521
T r a n s f o r m a t i o n s by G e n u s :
SPECIES
fellutanum
I i requentans *
*
funiculosum
fuscum *
gladioli
godlewskii *
granulatum
helicum
herquei
humuli
implicatum *
islandicum
ital icum
janthinellum *
SOURCE
MCC
SSSR
ASRI
ATCC-10444
CZAS
MCC
MCC
NRRL
CZAS
MCC
CZAS
CZAS
MCC
CZAS
MCC
ASRI
CZAS
MCC
FCUTS
MCC
MCC
CZAS
MCC
ASRI
SUBSTRATE
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnejie -3 ,20-dione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ? 20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
REACTION
none at C - l l
-
17/3-Ac-17a-o x a - 1 7 - C = 0
17/3-Ac-1 7 - C = 0
17/3 - A c - 17a-o x a - 1 7 - C = 0
none at C - l l
none at C - l l
-
-
-
17/3-Ac-17a-o x a - 1 7 - C = 0
none at C - l l
17/3-Ac-17a-o x a - 1 7 - C = 0
-
none at C - l l
-
none at C - l l
-
-
none at C - l l
17/3-Ac-17a-o x a - 1 7 - C = 0
none at C - l l
none at C - l l
-
none at C - l l
17/3-Ac— 17a-o x a - 1 7 - C = 0
R E F .
D-190
C-99
C-99
M-637
C-99
D-190
D-190
M-587
M-587
M-587
C-99
D-190
C-99
C-99
D-190
C-99
D-190
C-99
C-99
D-190
C-99
D-190
D-190
C-99
D-190
C-99
522
TABLE I I I
PENICILLIUM
TABLE I I I
Transformat ions by Genus: PÉNICILLIUM
SPECIES
janthinellum
javanicum *
*
jenseni i *
*
*
*
kapuscinskii *
lanoso-coeru leum
lanoso-gr i seum
lanoso-vir ide
lanosum
lavendulum
SOURCE
ATCC-10455
CZAS
MCC
ASRI
CZAS
MCC
NRRL
ASRI
CZAS
FCUTS
MCC
SSSR
SSSR
MCC
NRRL
MCC
MCC
CZAS
ASRI
NRRL
SUBSTRATE
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4-dehydrotigogenone
REACTION
oxidation -products not identified
17/3-Ac-17a-oxa-17-C = 0
none at C - l l
17/3-Ac-17a-oxa-17-C = 0
17/3-Ac-17a-o x a - 1 7 - C = 0
none at C - l l
-
-
-
17/3-Ac-17a-o x a - 1 7 - C = 0
17/3-Ac-17a-oxa-17-C = 0
17/3-Ac— 17a-o x a - 1 7 - C = 0
none at C - l l
17/3-Ac-17a-o x a - 1 7 - C = 0
17/3-Ac—17a-o x a - 1 7 - C = 0
none at C - l l
-
-
-
none at C - l l
none at C - l l
-
-
-
-
-
R E F .
M-602
C-99
D-190
C-99
C-99
D-190
M-587
M-587
M-587
C-99
C-99
C-99
D-190
C-99
C-99
D-190
M-587
M-587
M-587
D-190
D-190
C-99
C-99
M-587
M-587
M-587
523
524
TABLE I I I
Transformations by Genus: PÉNICILLIUM
SPECIES SOURCE SUBSTRATE REACTION R E F .
levitum
lilacinum
ASRI
CZAS
ASRI
ATCC-10114
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
17ß-hydroxy-4-andros ten-3-one
4 -andros tene-3 ,17-d ione
5a -p regnane -3 ,11 ,20 - t r i one
5ß -p regnane -3 ,12 ,20 - t r ione
3α, 11α, 17a-tr ihydroxy-5/3-pregnan-20-one
4-pregnene-3 ,20-d ione
14a-hydroxy-4-pregnene-3 ,20 -dione
17a-hydroxy-4-pregnene-3 ,20-dione
14a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene-3,20-dione
11a, 17a ,21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
17/3-Ac^l7a-oxa-17-C = 0
17/3-OH-> 1 7 - C = 0
17/3-OH-17a-o x a - 1 7 - C = 0
17/3-OH-*13,17-seco-13a-OH-16-COOH
17-C = 0—17a-oxa-17-C = 0
1 7 - 0 = 0 - 1 3 , 1 7 -seco-13a-OH-16-COOH
17/3-Ac — 1 7 - C = 0
17/3-Ac — 1 7 - C = 0
17a-OH-17ß-Ac - 1 7 - C = 0
oxidation -products not identified
2 0 - C = O -20ß-OH
17j3-Ac-17-C = 0
17/3-Ac->17-C = 0
17a-OH-17/3-Ac - 1 7 - C = 0
17/3-(20-C = O-21-OH)—17-C=C|
17a-OH-17/3-(20-C=O-21-OH)| -»17 -C=0
20-C=O->20/3-OH
17a-OH-17/3-(20-C = O-21-OH)| ->17-C=0
C-99
C-99
C-99
P-737
P-737
P-737
P-737
P-737
M-637
M-637
M-637
M-602
M-637
M-637
E-204; M-637
M-637
M-637
M-637
M-637
M-637
TABLE I I I
Transformat ions by Genus: PÉNICILLIUM
525
SPECIES
li lacinum
*
*
(in mixed cul ture with 1 Rhizopus n igr icans
[ l la -OH])
(in mixed cul ture with Rhizopus n igr icans [ l l a -OH])
SOURCE
ATCC-10114
CZAA
CZAS
MCC
NRRL
UC
SUBSTRATE
14a, 17c*,21-tr ihydroxy-4-preg-nene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3 ,11 ,20- t r ione
17ce,21-dihydroxy-4-pregnene-3 ,11 ,20- t r ione 21-aceta te
3 -ketobisnor -4 -cholen-22 -al
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
4 -p regnene-3 ,20-d ione
l l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
4 -p regnene-3 ,20-d ione
l l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
REACTION
17α-ΟΗ-17β-(20-C=O-21-O H ) - 1 7 - C = 0
17a-OH-17/3-(20-C=O-21-OH)-*17-C=0
17tf-OH-17/3-(20 -C=O-21-0 A c ) - 1 7 - C = 0
20-H-C = O -20/3-CH2OH
170-Ac—17a-oxa-17-C = 0
17/3-Ac—17a-o x a - 1 7 - C = 0
l l a - O H
-
-
-17/3-Ac->17a-o x a - 1 7 - C = 0
17/3 - A c ^ 17/3-OH
17/3-Ac^l7-c=o 17/3-Ac->17a-o x a - 1 7 - C = 0
17/3-Ac-17/3-OH
20-C=O -20/3-OH
17/3-Ac -17-C = 0
17/3-Ac—17-c=o
17/3-Ac— 17-C = 0
R E F .
M-637
M-637
M-637
E-202; W-1068
C-99
C-99
D-109
M-587
M-587
M-587
P -726 ; S-832
S-832
P -726 ; S-832
S-832
S-832
S-832
S-831; S-83_2_
S-831
S-831
526
TABLE I I I
Transformat ions by Genus: P É N I C I L L I U M
SPECIES
lividum
*
luteum
mar tens i i
melearginum *
*
melinii *
miczynskii *
*
multicolor *
*
nalgiovensis
*
SOURCE
ATCC-10102
MCC
SSSR
ATCC-10465
CZAS
FRI
CZAS
MCC
ASRI
CZAS
MCC
CZAS
MCC
CZAS
FCUTS
MCC
FCUTS
SSSR
MCC
SSSR
SUBSTRATE
21-hydroxy-4 -p regnene -3 ,20 -dione aceta te
(revision of s t ruc tu re -20a to 20j3 - Ref. S-832)
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
17ö ,21-d ihydroxy-4-pregnene-3,20-dione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
REACTION
17/3-(20-C=O-21-OAc) -1 7 - C = 0
20-C=O -> 20/3-OH;21-OAc - 2 1 - O H
none at C-11
17/3-Ac-17a-o x a - 1 7 - C - O
oxidation -products not identified
-
-
-
none at C-11
1 7 / 3 - A c - 1 7 a -o x a - 1 7 - C = 0
17/3-Ac— 17a-o x a - 1 7 - C = 0
none a t C-11
17/3 - A c - 17a-o x a - 1 7 - C = 0
none at C-11
17/3-Ac—17a-o x a - 1 7 - C = 0
17/3-Ac— 17a-o x a - 1 7 - C = 0
none at C-11
17/3-Ac-17a-o x a - 1 7 - C = 0
17/3-Ac-17a-o x a - 1 7 - C = 0
none a t C-11
17/3-Ac— 17a-o x a - 1 7 - C = 0
R E F .
M-637
M-637
D-190
C-99
M-602
C-99
S-849
C-99
D-190
C-99
C-99
D-190
C-99
D-190
C-99
C-99
D-190
C-99
C-99
D-190
C-99
TABLE I I I
Transformat ions by Genus: PÉNICILLIUM
527
SPECIES
namyslowskii
n igr icans *
*
*
notatum *
1 *
1 *
(Wastling)
SOURCE
MCC
ASRI
ATCC-10115
CZAA
CZAS
MCC
ASRI
ATCC-9479
CZAS
FAR MIT
FCUTS
IPB
SUBSTRATE
4-pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
(revision of s t r uc tu r e -20a to 20/3 - Ref. S-832)
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
4 -pregnene-3 ,20-d ione
5-androstene-3/3,17a-diol
5-androstene-3/3 ; 17/3-diol
4 -andros tene -3 ,17-d ione
4 - p r e g n e n e - 3 , 2 0 - d i o n e
1 l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
REACTION
none at C - l l
17j3-Ac-»17a-o x a - 1 7 - C = 0
oxidation -products not identified
17/3-(20-C=O-21-OH) -> 1 7 - C = 0
20-C=O-> 20/3-OH
17/3-Ac-17a-o x a - 1 7 - C = 0
17/3-Ac-»17a-o x a - 1 7 - C = 0
none at C - l l
17/3-Ac-17/3-OH
oxidation -p roduc t s not identified
17/3-Ac — 17ß-OH
15«-OH
3-C = 0—3/3-OH; Δ 4 - 5 α - Η
15α -OH
17β-Ac-17/3-OH
3/3-OH-3-C=0· , . 5 . 4 Δ -*Δ
3 / 3 - O H - 3 - C = 0 ; Δ 5 - Δ 4
1 7 - C = 0 -17/3-OH
17/3-Ac -17/3-OH
17/3-Ac — 17/3-OH
R E F .
D-190
C-99
M-636
M-637
M-637
C-99
C-99
D-190
C-99
M-602
C-99
C-86
C-86
C-86
C-99
H-337
H-337
H-336
H-332; H-336
H-336 1
528
TABLE I I I
Transformations by Genus: PÉNICILLIUM
SPECIES
nota tu m *
novae-zeelandia
ochraceum
ochro-chlorum *
*
olivino-viride
oxalicum
*
*
pali tans
pallidum
parvum *
SOURCE
IPB
MCC
NG
(Sandoz-831)
ATCC-10473
CZAS
FCUTS
MCC
ASRI
CZAS
MCC
MCC
ATCC-10576
CZAS
FCUTS
MCC
CZAS
MCC
ASRI
ASRI
SUBSTRATE
17a-hydroxy-4-pregnene-3 ,20-dione
4 -p regnene -3 ,11 ,20 - t r i one
4-pregnene-3 ,20-d ione
5-choIesten-3j3-oi (sole carbon source)
24/3-methyl -5 ,7 ,22-choles ta-trien-3/3-ol (sole carbon source)
3j8, 6ß? 8j3,14ß-tetrahydroxy-4-20,22 -bufatrienolide 6-aceta te 3-glucoside
3/3,14/3-dihydroxy -5/3-20(22)-car denolide - 3 - [glucosyl -digitoxosyl -digitoxosyl -digitoxoside ]
5/3-pregnane-3, 6 ,20- t r ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -p regnene-3 ,2 0-dione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
REACTION
17a-OH-17/3-Ac->17j3-OH
17/3-Ac-*17/3-OH
none at C - l l
utilization
utilization
3/3-[l ξ -gluco-sidel —» 3/3-OH
glucosyl-digitoxosyl-digitoxosyl-digitoxoside —* digitoxosyl-digitoxosyl-digitoxoside
17j3-Ac-»17-C=0
oxidation -products not identified
--
none at C - l l
17/3-Ac-* 17a-o x a - 1 7 - C = 0
17/3-Ac-17a-o x a - 1 7 - C = 0
none at C - l l
none at C - l l
oxidation -products not identified
l l a - O H
11a-OH
none a t C - l l
-none at C -11
-
17/3-Ac-17a-o x a - 1 7 - C = 0
R E F .
H-336
H-336
D-190
S-793c
S-793c
S-936a
S-936a
M-637
M-602
C-99
C-99
D-190
C-99
C-99
D-190
D-190
M-636
C-99
C-99
D-190
C-99
D-190
C-99
C-99
T r a n s f o r m a t i o n s by G e n u s :
SPECIES
parvum *
patulum
phoenicum
p i sca r ium *
psi t tacinum *
puberulum
pulvil lorum *
1 *
purpurescens *
purpurogenum
pusil lum *
1 *
rac iborsk i i *
1 *
SOURCE
FCUTS
NG (Sandoz-815)
FCUTS
CZAS
MCC
CZAS
ASRI
MCC
ASRI
CZAS
CZAS
MCC
SSSR
ASRI
CZAS
MCC
FCUTS
SSSR
ASRI
CZAS
SUBSTRATE
4-pregnene-3 ,20-d ione
3/3, 6/3, 8/3,14/3-tetrahydroxy -4 , 20,22 -bufatrienolide 6-aceta te 3-glucoside
3ß,14/3-dihydroxy-5/3-20(22)-cardenolide 3-[glucosyl-digitoxosy 1 -digitoxosy 1 -digitoxoside ]
4 -p regnene-3 ,20-d ione
4 -p regnene-^ , 20-dione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
REACTION
17/3-Ac-17a-o x a - 1 7 - C = 0
3/3-[lVgluco-side ) — 3/3-OH
glucosyl-digitoxosyl-digitoxosyl-digitoxoside— digitoxosyl-digitoxosyl-digitoxoside
17/3-Ac-17a-o x a - 1 7 - C = 0
none at C-11
17/3-Ac-17a-o x a - 1 7 - C = 0
-
none at C-11
17/3-Ac-17a-o x a - 1 7 - C = 0
17/3-Ac-17a-o x a - 1 7 - C = 0
17/3 - A c - 17a-o x a - 1 7 - C = 0
none at C-11
17/3-Ac-17a-o x a - 1 7 - C = 0
-
-
none at C-11
17/3-Ac-17a-o x a - 1 7 - C = 0
17/3-Ac— 17a-o x a - 1 7 - C = 0
1 7 ß - A c - 1 7 a -o x a - 1 7 - C = 0
17/3-Ac-17a-oxa -17 -C^O
R E F .
C-99
S-936a
S-936a
C-99
C-99
D-190
C-99
C-99
D-190
C-99
C-99
C-99
D-190
C-99
C-99
C-99
D-190
C-99
C-99
C-99
C-99
TABLE I I I
PENICILLIUM
529
SPECIES
ra i s t r i ck i i *
*
*
r e s t r i c t u m *
*
*
r e s t r i c tu losum *
*
rolfsi i
roquefort i
1 ro seo -pu rpureum
rubrum
1 rugulosum *
*
sc le ro t io rum *
SOURCE
ASRI
ATCC-10490
CZAA
CZAS
MCC
ASRI
CZAS
FCUTS
MCC
ASRI
CZAS
-MCC
CZAS
FCUTS
MCC
NRRL
MCC
CZAS
ASRI
CZAS
MCC
SSSR
SUBSTRATE
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
REACTION
17/3-Ac->17a-o x a - 1 7 - C = 0
oxidation -products not identified
17/3-Ac-17a-o x a - 1 7 - C = 0
17/3-Ac->17a-o x a - 1 7 - C = 0
none at C - l l
17/3-Ac-17a-o x a - 1 7 - C = 0
17/3-Ac—17a-o x a - 1 7 - C = 0
17/3-Ac->17a-o x a - 1 7 - C = 0
none at C - l l
17/3-Ac-17a-o x a - 1 7 - C = 0
17/3-Ac-17a-o x a - 1 7 - C = 0
none at C - l l
-
-
none at C - l l
-
-
-
none a t C - l l
-
15/3-OH
15/3-OH
none at C - l l
17/3-Ac— 17a-o x a - 1 7 - C = 0
R E F .
C-99
M-602
C-99
C-99
D-190
C-99
C-99
C-99
D-190
C-99
C-99
D-190
C-99
C-99
D-190
M-587
M-587
M-587
D-190
C-99
C-99
C-99
D-190
C-99
530
T r a n s f o r m a t i o n s by Genus:
TABLE I I I
PENICILLIUM
TABLE I I I
Transformat ions by Genus: PÉNICILLIUM
531
SPECIES
s impl ic i s s imum *
solitum
soppi *
species
SOURCE
CZAS
MCC
MCC
CZAS
MCC
ATCC-11598
ATCC-12556
SUBSTRATE
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
17j3-hydroxy-4-estren-3-one
D -homo -17a - oxa -1 ,4 -andr osta -d iene-3 ,17-d ione
4 -pregnene-3 ,20-d ione
3a-hydroxy-5/3-androstan-17-one
5a -andr ostane -3 ,17 -dione
5/3-androstane-3,17-dione
17/3-hydroxy-4-androsten-3-one
3/3-hydroxy- 5 -andr osten -17 -one
4 -andr ostene -3 ,17 -dione
REACTION
17/3-Ac-17a-o x a - 1 7 - C = 0
none at C-11
none at C-11
17/3-Ac-17a-oxa-17-C = 0
none at C-11
15α-OH; 17/3-OH-17-C = 0
15a-OH
15a-OH
15a-OH
products of un-known or questionable s t ruc tu re
7/3-OH
la -OH
7/3-OH
la-OH
6/3-OH
12/3-OH
15/3-OH
la,6/3-diOH
la-OH
la -OH; 3/3-OH-> 3-C=0;A5—Δ4
l a - O H
2/3-OH
R E F .
C-99
D-190
D-190
C-99
D-190
D-151
D-151
D-158
F-285; F-287
F-285; F-287
F-290
D-163
F-290
T-1036
T-1036
T-1036
T-1036
T-1036
D-163; D-164; D-168; G-293
D-163; D-168
D-163; D-167; D-168
D-163; D-167; D-168
532
T A B L E I I I
T r a n s f o r m a t i o n s by Genus : PÉNICILLIUM
SPECIES SOURCE SUBSTRATE REACTION R E F .
species ATCC-12556
ATCC-13001
EM
IPB
NG
4-andros tene-3 ,17-d ione
17a-oxa-D-homo-4-andros tene-3,17-dione
4-pregnene-3 ,20-d ione
16a, 17α-oxido-4-pregnene -3, 20-dione
17/3,21-dihydroxy-4-pregnene-3,20-dione
lia -methyl -5 - a n d r o s t e n - l a , 3β, 17/3-triol
17a, 21 - tr ihydroxy -16 -methylene-1 ,4-pregnadiene-3 , 20-dione
17a-hydroxy-4-pregnene-3 ,20-dione
1,3, 5(10)-estrat r iene-3,17/3-diol (sole carbon source)
3 - h y d r o x y - l , 3 , 5 (10) -es t ra t r ien-17-one (sole carbon source)
3a-hydroxy-5/3-cholanic acid (sole carbon source)
la -OH; D-163 5a-H
1α-ΟΗ; Δ — 5a-H; 3-C = 0— 3/3-OH
2/3-OH
2/3-OH
15/3-OH
2/3,15/3-diOH
7/3,15/3-diOH
6/3-OH;15-C = 0 (via 15/3-OH)
7/3-OH
7/3-OH
15/3-OH
3/3-OH->3-C = 0 : Δ 5 - Δ 4
11α-OH
1 7 - C = 0 — 17/3-OH
17/3-Ac-17-C = 0
17/3-Ac-» 17a-oxa-17-C = 0
15β-ΟΗ
llff-OH
17/3-Ac-17/3-OH
17a-OH-17/3-
D-163
T-1036
T^1036
T^1036
T-1036
D-177; T-1036; T-1037
T-1036
T-1036
T-1036; T-1037
T-1036
G-293
M-558
H-336
C-102
C-99; C-102
C^99
C-99; D-190
C-99; C-102; H-336 H-336
Ac—17/3-OK
utilization
T-1033
T-1033
T-1033
4-andros tene-3 ,17-d ione
4-pregnene-3 ,20-d ione
TABLE I I I
Transformations by Genus: PÉNICILLIUM
533
SPECIES
species
(in mixed culture with Rhizopus n igr icans | l l a - O H | - Sporotr ichum su l lu rescens [ l la-OH|)
spicul isporum
spinulosum *
SOURCE
NC
(Sandoz-822, 825,833,834, 838 ,841 ,851 , 858.860,889, 890,909)
(Sandoz-822, 833 ,834,838, 851 ,858,889, 909)
(Sandoz-858, 889)
(Univ. of Texas - Sp. 17 ,18 ,19 ,20)
NG
NRRL
Sear le
SQ
UC
CZAS
ASRI
SUBSTRATE
3a, la, 12a-tr ihydroxy-5/3-cholanic acid (sole carbon source)
3/3, 6/3, 8/3,14/3-tetrahydroxy-4, 20,22 -bufatrienolide 6-aceta te 3-glucoside
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide - 3 -1 glucosy1-digitoxosyl-digitoxosyl-digitoxoside ]
Digilanid A
5 -cholesten -3/3 -ol (suggested precaut ions to be taken before concluding s t e ro l is modified by a culture)
4 -p regnene-3 ,20-d ione
plant saponins
3/3 -hydr oxy - 5 -androsten -17 -one
4 -andros tene -3 ,17-d ione
1 7 a - o x a - D - h o m o - l , 4 - a n d r o s t a -d iene-3 ,17-d ione
4 -pregnene-3 ,20-d ione (revision of s t ruc tu re -20a to 20/3 - Ref. S-832)
21 -hydroxy-4 -p regnene -3 ,20 -dione aceta te (revision of s t ruc tu re - 20a to 20/3- R e t S-832)
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
REACTION
utilization
3ß-[lVgIuco-side]^3/3-OH
glucosyl-digitoxosyl-digitoxosyl-digitoxoside —» digitoxosyl-digitoxosyl-digitoxoside
select ive c leav-age of glucose from sugar chain
util ization
17ß-Ac->17-C-0
hydrolysis of glycosides to agiycones (sapogenin)
1 α - Ο Η ; Δ 5 - Δ 4 ; 3/3-OH-3-C = 0
1α-ΟΗ; 2/3-ΟΗ
15a-OH
20-C = O -20/3-OH
20-C = O -20/3-OH; 2 1 -O A c - 2 1 -OH
-17/3-Ac—17a-oxa-17-C = 0
R E F .
T-1033
S-936a
S-936a
S-936a
P-732
S-922
K-478
D-162
D-162
P-706
M-637
M-637
C-99
C-99
534
TABLE I I I
Transformat ions by Genus: P É N I C I L L I U M
SPECIES
spinulosum *
*
steckii *
*
*
* *
stoloniferum
s t r i a tum
subalter itium *
*
t a rdum
* ter l ikowski *
t e r r e s t r e
thomii *
*
*
SOURCE
CZAA
CZAS
MCC
ASRI
CZAS
FCUTS
I P ß
MCC
SSSR
SSSR
CZAS
ASRI
FCUTS
MCC
SSSR
ASRI
MCC
ASRI
CZAS
MCC
ASRI
ATCC-10506
CZAS
FCUTS
MCC
SUBSTRATE
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
l i a , 17a-dihydroxy-4-pr egnene -3,20-dione
1 l a , 17a -dihydroxy -4 -pr egnene -3,20-dione
l i a , 17a-dihydroxy-4-pregnene -3,20-dione
l i a , 17a-dihydroxy -4 -pregnene -3,20-dione
REACTION
17/3-Ac-17a-o x a - 1 7 - C = 0
17/3-Ac-17a-o x a - 1 7 - C = 0
none at C-11
17/3-Ac-17a-o x a - 1 7 - C = 0
17/3-Ac— 17a-oxa-17-C = 0
17/3-Ac-17a-o x a - 1 7 - C = 0
17ß-Ac-17-C = 0
17/3-Ac-17a-oxa-17-C = 0
none a t C-11
17/3-Ac—17a-o x a - 1 7 - C = 0
--
17/3-Ac-17a-o x a - 1 7 - C = 0
17/3-Ac-17a-o x a - 1 7 - C = 0
l i a - O H
15/3-OH
17/3-Ac-17a-o x a - 1 7 - C = 0
none at C-11
--
none a t C-11
17/3-Ac-17a-o x a - 1 7 - C = 0
oxidation -products not identified
170-OH-17/3-A c - 1 7 - C = 0
17a-Ac— 17a-o x a - 1 7 - C = 0
17a-Ac— 17a-o x a - 1 7 - C = 0
none at C-11
R E F .
C-99
C-99
D-190
C-99
C-99
C-99
C-102
C-102
D-190
C-99
C-99
C-99
C-99
C-99
D-190
C-99
C-99
D-190
C-99
C-99
D-190
C-99
M-602
M-637
C-99
C-99
D-190
TABLE I I I
Transformat ions by Genus: P É N I C I L L I U M
535
SPECIES
thomii
t rzebinski i
turbatum
ur t icae
var iabi le
vermicula tum
ver rucu losum
vinaceum
1 vi r id ica tum
waksmanni
wortmanni
SOURCE
WISC
MCC
MCC
ATCC-10120
CZAA
CZAS
ASRI
MCC
NRRL
MCC
MCC
CZAS
MCC
MCC
MCC
SUBSTRATE
14/3,19-dihydroxy-3-keto-4, 20(22) -car dadienolide
14/3-hydroxy-3,19-dioxo-4, 20(22) -car dadienolide
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
17j3-hydroxy-4-estren-3-one
17/3-hydroxy-4-androsten-3-one
4 -pregnene-3 ,20-d ione
4 - p r e g n e n e - 3 , 1 1 , 20- t r ione
6a - f l uo ro -4 -p regnene -3 ,11 , 20-tr ione
9 a - f l u o r o - 4 - p r e g n e n e - 3 , 1 1 , 20- t r ione
6û! -methyl -4-pregnene-3 ,11 , 20- t r ione
6α ,9α-d i f luoro-4-pregnene-3 , 11, 20- t r ione
9a - f luo ro -6a -me thy l -4 -p reg -nene -3 ,11 ,20 - t r i one
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 - p r e g n e n e - 3 , 20-dione
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
REACTION
1 9 - O H -19-C = 0
1 9 - C = 0 -19-OH
none a t C-11
none a t C-11
15f-OH
15α-OH
15û-OH
6/3-OH
15α -OH
15α-OH
15α-OH
15α-ΟΗ
15α-OH
15α-OH
--
-none a t C-11
---
none at C-11
none at C-11
-none at C-11
none a t C-11
none at C-11
R E F .
S-892
S-892
D-190
D-190
M-639
M-639
E-202; F-250; M-576; M-577; M-602
E-202
A-31 ; ß - 4 4
A-31
A-31
A-31
A-31
A-31
C-99
C-99
C-99
D-190
M-587
M-587
M-587
D-190
D-190
C-99
D-190
D-190
D-190
536
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by G e n U S : PENTATRICHOMONAS (Zoomastigina - Polymastigina) PESTALOTIA (Imperf. - Melanconiales)
SPECIES
PENTATRICHOMONAS (Protozoa)
gal i inarum
hominis
! PESTALOTIA
diospyri
foedans
funerea
royenae
SOURCE
uc
uc
FRI
ATCC-11817 (QM-795)
AY
C
KSC
C
KSC
TNAES
ATCC-11816 (QM-531)
SUBSTRATE
1 la -hydroxy-4-andros tene -3,17-dione
l , 4 - and ros t ad i ene -3 ,17 -d ione
1 ,4-andros tad iene-3 ,17-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4-pregnene-3 ,20-d ione
16a-ethyl-17a, 21-dihydroxy -1,4 -pregnadiene-3 ,20-dione 21-aceta te
1 la, 21 -dihydr oxy- 16a- methyl -1 ,4-pregnadiene-3 , 20-dione
17ö, 21 -dihydr oxy -4 -pr egnene -3, 20-dione (with spores)
11/3, 21-dihydroxy-3, 20-diketo-4-pregnen - 18-oic acid (18—» 11) lactone
17/3-hydroxy-4-androsten-3-one
3 /3-hydroxy-5a-pregnane- l l , 20-dione
4-pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3, 20-dione
4-pregnene-3 ,20-d ione
REACTION
17-C=0-> 17j3-OH
1 7 - C = 0 -17/3 -OH
17-C=0-> 17/3-OH
l l o - O H
11a-OH
l l a - O H ; 2 1 - O A c -21-OH
l l ö - O H
16G-OH
16a-OH
16a-OH
16a-OH
X-OH; 16a-OH
16a-OH
11a-OH
R E F .
S-830
S-830
S-830
S-849
S-882
O-703
O-702
S-835
W-1091
F-265; F-266
W-1092
F-266
F-265; F-266 S-849 1
S-882
537
TABLE I I I TAXONOMY
Transformat ions by Genus: ΡΕΖΓΖΑ PHIALOPHORA
PHOLIOTA PHOMA
(Asco. - Pez iza les ) (Imperf. - Moniliales) (3as id io . - Agaricales) (Imperf. - Sphaeropsidales)
SPECIES
PEZIZA
species
PHIALOPHORA
ve r rucosa
PHOLIOTA
adiposa
squar roso ides
PHOMA
species
SOURCE
C (ETH-M-23)
(ETH-M-26)
FRI
FRI
AL (H-140)
ATCC-13145
SUBSTRATE
21-hydroxy-4 -p regnene-3 ,20-dione
d, l -21-hydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
4-pregnene-3 ,20-d ione
1 6 a - t e r t - b u t y l - 1 7 a , 2 1 -d ihydroxy-5a-pregnane-3 , 20-dione
16/3-ethyl-17a,21-dihydroxy-5a-pregnane-3 ,20-d ione
17a, 21-dihydroxy-16a-methyl -5a-pregnane-3 ,20-d ione
17a, 21-dihydroxy-16/3-methyl-5a-pregnane-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
REACTION
7a-OH
d , l - d - 7 a - O H + 1
oxidation -products not identified
l l a - O H
11/3-OH
l l a - O H
l l ß - O H
l l a - O H
11/3-OH
l l a - O H
11/3-OH
6/3-OH
l l a - O H
11/3-OH
R E F .
M-585
W-1102
S-849
S-849
S-825
1-42.
1-422
1-422
1-422
1-422
1-422
1-422
1-422
1-422
1-422
1 -4 .72
538
T r a n s f o r m a t i o n s by G e n u s :
TABLE I I I
PHOMA PHOMOPSIS PHYCOMYCES
TAXONOMY
(Imperf. - Sphaeropsidales) (Phyco. - Mucorales)
SPECIES
species
PHOMOPSIS
c i t r i
PHYCOMYCES
blakesleeanus
SOURCE
ATCC-13145
FAHU
FRI
TNAES
NRRL
P F
SUBSTRATE
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a ,21-dihydroxy-16a-methyl -4-pregnene-3 ,20-d ione
17a,21-dihydroxy-16/3-methyl-4-pregnene-3 ,20-d ione
16ö-ter t . bu ty l -17a ,21 -dihydr oxy -1 ,4 -pr egnadiene -3,20-dione
16/3-ethyl-17a, 21-dihydr oxy -1,4 -pr egnadiene -3 ,20-dione
17a, 21-dihydroxy-16a-methyl -1,4 -pr egnadiene -3 ,20-dione
17a,21-dihydr oxy-16j3-me thy 1-1 ,4-pregnadiene-3 , 20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21 -d ihydroxy-4-pregnene-3, 20-dione
17a, 21-dihydr oxy-4-pregnene-3,20-dione
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
17a ,21-d ihydroxy-4 ,14-pregnadiene-3 ,20-d ione
REACTION
15/3-OH
l l a - O H
11/3-OH
l l a - O H
11/3-OH
l l a - O H
11/3-OH
l l a - O H
11/3-OH
l l a - O H
11/3-OK
l l a - O H
11/3-OH
l l a - O H
Δ14 - 1 4 a , 15a-oxide
R E F .
1-422
1-422
1-422
1-422
1-422
1-422
1-422
1-422
1-422
1-422
1-422
1-422
1-422
S-849
S-849
S-849
M-587
M-587
M-587
S-865
TABLE I I I
T r a n s f o r m a t i o n s by Genus : PHYCOMYCES
539
SPECIES
blakesleeanus
nitens
pirot t ianus
1 species
SOURCE
SQ
UC
SSSR
SSSR
ATCC-14163
SUBSTRATE
3/3-hydroxy-5-pregnen-20-one
4 - p r e g n e n e - 3 , 20-dione
4 -p regnene-3 ,20-d ione
17a-hydroxy-4-p regnene-3 , 20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
1 7a, 21 -dihydroxy- 4 -pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3, 20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
4 -p regnene-3 ,20-d ione
1 l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
l l / 3 ,17ö ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
17a, 21-dihydroxy-9/3,11/3-oxido-4-pregnene-3 ,20-d ione
9a - f luo ro - l l / 3 ,16α ,17α ,21 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione 16,17-acetonide
9ö-f luoro- l l /3 ,16α, n a ^ l - t e t r a -h y d r o x y - l ^ - p r e g n a d i e n e -Sj 20-dione 16,17-acetonide
17a, 21 -dihydroxy-4 -pregnene -3 ,11 ,20 - t r ione
9a-f luoro-16a, 17a, 21 -tr ihydroxy-4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e 16,17-acetonide
REACTION
Δ 5 - Δ 4 ; 3/3-ΟΗ ->3-C = 0
7a-OH
15/3-OH
11 -oxygénation
11-oxygénation
11-oxygénation
11-oxygénation
Πα-ΟΗ
-
6/3-OH
6/3-OH
6/3-OH
6/3-OH
6/3-OH
6/3-OH
6/3-OH; 11/3-OH
-n-c=o 6/3-OH
6/3-OH
6/3-OH
R E F .
P-710
F-285; F-286; F-288
F-285; F-286; F-287; F-288
M-601; M-636
M-601; M-636
M-601; M-636
M-601; M-636
E-224
E-224
H-400
H-400
H-400
H-400
H-400
H-400
H-400
H-400
H-400
H-400
540
T r a n s f o r m a t i o n s by G e n u s :
TABLE I I I
PHYCOMYCES PHYTOMONAS PHYTOPHTHORA
PICHIA
TAXONOMY
(Schizo0 - Pseudomonadales) (Phyco. - Peronospora les ) (Asco. - Endomycetales)
SPECIES
species
theobromatus
PHYTOMONAS (see Xanthomonas)
c i t r i
e icobatryae
malvacearum
PHYTOPHTHORA
ci trophthora
paras i t i ca
PICHIA
membranaefaciens
rosa
SOURCE
NG
UC
TNAES
TNAES
NG
TNAES (CI-16)
FAKU
NRRL
FRI
SUBSTRATE
5-cholesten-3/3-ol (sole carbon source)
24/3-methyl-5, 7 ,22-cho les ta -trien-3/3-ol (sole carbon source)
4 -pregnene-3 ,20-d ione
1 7a -hydroxy-4 -p regnene -3 ,20 -dione
21-hydroxy-4-p regnene-3 ,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
5 -cholesten -3/3-ol (sole carbon source)
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
17a, 21-dihydroxy-4-pregnene-3,20-dione
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
REACTION
utilization
utilization
11-oxygénation
11-oxygénation
11-oxygénation
11-oxygénation
—
-
—
-
—
-
-
-
REF.
S-793c
S-793c
M-601; M-636
M-601; M-636
M-601; M-636
M-601; M-636
S-849
S-849
T-1030
S-849
S-849
M-587
M-587
M-587
S-849
541
T r a n s f o r m a t i o n s by G e n u s :
TABLE I I I
PILAIRA PIRICULARIA
PLEOSPORA
TAXONOMY
(Phyco. - Mucorales) vlmperf. - Moniliales) (Asco0 - Sphaeriales)
SPECIES SOURCE SUBSTRATE REACTION
PILAIRA
anomala
PIRICULARIA
oryzae
PLEOSPORA
gaeumanni
NRRL
FAKU
FRI
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
17a ,21-dihydroxy-4-pregnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
l l /3 -hydroxy-3 ,20-d ike to-4-preg-nen-18-oic acid (18 -* 11) lactone
11/3,21 -dihydroxy -3 ,20 -diketo-4 -p regnen-18-a l
d, 1-21-hydroxy-4-pregnene-3, 20-dione
12a - f l uo ro - l lß -hyd roxy -4 -p reg -nene -3 ,20-dione
12a-fluoro-11/3,17a-dihydroxy -4 -pregnene-3 ,20-d ione
9a-f luoro-11/3,17a,21-tr ihydroxy-4-pr egnene-3 ,20-dione
I 9a - f l uo ro -4 -p regnene -3 ,11 ,20 -tr ione
l l /3 ,21-d ihydroxy-3 ,20-d ike to-1,4 -pr egnadien -18 -al
12a-f luoro-l l /3 ,17a-dihydroxy -l , 4 - p r e g n a d i e n e - 3 , 20-dione
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy-1,4 -pr egnadiene - 3 , 2 0 - dione
6/3-OH
6/3-OH;lla-OH
11a-OH
14a-OH
14a
d,l-+ 1
14a
14a
14a
14a
14a
14a
14a
-OH
-d-14a-OH
-OH
-OH
-OH
-OH
-OH
-OH
-OH
W-
w-
vV-
w-
w-
w-
w-
w-
w-
-1108
-1108
-1102
-1103
-1103
-1108a
-1108a
-1108
-1103
-1108a
S
c
R E F .
M-587
M-587
M-587
S-849
S-849
S-849
542
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by G e n u s : PLEUROTUS PLUTEUS
POLYPORUS
(Basidio. - Agaricales) (ßasidio. - Agaricales) (Basidio. - Agaricales)
SPECIES
PLEUROTUS
japonicus
os t rea tus
PLUTEUS
granular is
POLYPORUS
abietinus
brumal i s
caeruleoporus
cinnabar inus
conchifer
frondosus
pubescens
radica ta
SOURCE
IAM
FAKU
FRI
NRRL-2366
AL(C-123)
UC
AL(G-67)
AL(H-126)
AL(G-90)
LED (D-6)
AL(C-255)
IAM
IAM
AL(H-139)
SUBSTRATE
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
17a,21 -dihydroxy -4 -pr egnene -3,20-dione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
not given
4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
21-hydroxy-4-pregnene-3 ,20-dione
4-pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy-4-pr egnene -3,20-dione
4-pregnene-3 ,20-d ione
REACTION
-
-
-
oxidation -products not identified
17ß-Ac->17a-o x a - 1 7 - C = 0
oxidation
oxidation -products not identified
oxidation -products not identified
oxidation -products not identified
6/3-OH; 14a-OH; 15/3-OH
oxidation -products not identified
-
6j3-OH;lla-OH
oxidation -products not identified
R E F .
S-849
S-849
S-849
R-778
S-825
M-601; M-636
S-825
S-825
S-825
B-63
S-825
S-849
S-849
S-825
543
TABLE I I I
T r a n s f o r m a t i o n s by G e n u s : POLYPORUS POLYSTICTUS
PORIA
TAXONOMY
(Basidio. - Agaricales) (Basidio. - Agar icales)
SPECIES
squamosus
sulfureus
tulipiferus
POLYSTICTUS
cinnabar ius
h i r s tus
polyzonus
1 sanguineus
vers ico la
vers ico lorpus
PORIA
cocos
I species
SOURCE
AL (C-180)
AL (C-6)
LAM
ATCC-13489
FAKU
IAM
IAM
IAM
FRI
IAM
S
S
ATCC-13490
FRI
SUBSTRATE
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihy droxy -4 -pregnene -3, 20-dione
17a, 21 -dihydroxy -4 -pregnene -3, 20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21 -dihydroxy-4-pregnene -3, 20-dione
17a ,21-d ihydroxy-4-pregnene-3 ; 20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
4 -pregnene-3 ,20-d ione
17a -hydroxy-4 -p regnene-3 ,20-3,20-dione
17a, 21 -dihydroxy -4 -p regnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
21-hydroxy-4-p regnene-3 , 20-dione
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
REACTION
oxidation -products not identified
oxidation -products not identified
—
6/3-OH;14a-OH; 15j3-OH
6j3-OH
14a-OH
15j3-OH
-
-
6j3-OH; l l a - O H
-
l l a - O H
l l a - O H
-
-
6/3-OH; l l a - O H
6ß-OH; l l a - O H
6/3-OH; 14a-OH; 15/3-OH
6^-OH
14a-OH
15j3-OH
—
R E F .
S-825
S-825
S-849
B-63
B-63
B-63
3-63
S-849
S-849
S-849
S-849
S-849
S-849
S-859
S-859
S-859
S-849
B-63
B-63
B-63
B-63
S-849
544
T r a n s f o r m a t i o n s by Genus :
TABLE I I I TAXONOMY
PORIA PROACTINOMYCES (Schizo. - Actinomycetales)
SPECIES
PORIA
vaporar ia
PROACTINOMYCES (Synonym - Nocardia)
act inomorphus
ag re s t i s
aquosus
coeliacus
crystal lophagus
erythropoi is
SOURCE
FRI
NG
NG
NG
NG
NG
NG
SUBSTRATE
1 la, 21 -dihydroxy -4 -pr egnene -3,20-dione
5-cholesten-3/3-ol (sole carbon source)
5-cholesten-3/3-ol (sole carbon source)
5-cholesten-3/3-ol (sole carbon source)
5-cholesten-3/3-ol (sole carbon source)
5-choles ten-3ß-ol (sole carbon source)
l ,3 ,5 v 10) -es t ra t r i ene-3 ,17 /3-d io l
5-androstene-3/3, 17/3-diol
3/3-hydroxy-5-androsten-17-one
17/3-hydroxy-4-androsten-3-one
3/3-hydroxy-5-cholenic acid
3-keto-4-cholenic acid
3/3-hydroxy-4-cholenic acid
5/3-cholestan-3/3-ol
5-cholesten-3/3-ol
REACTION
utilization
utilization
utilization
utilization
utilization
17/3-OH — 1 7 - C = 0
Δ5 - Δ 4 ; 3/3-OH — 3-C = 0
Δ 5 - Δ 4 ; 3 /3-OH-3-C = 0 ; 17/3-OH - 1 7 - C = 0
Δ 5 - Δ 4 ; 3/3-OH -3-C = 0
17/3-OH-1 7 - C = 0
Δ 5 - Δ 4 ; 3/3-OH -3-C = 0
17/3-CH (CH3)CH2CH2 COOH -17/3-COOH
3/3-OH-3 - C = 0
3/3-OH — 3 - C = 0
Δ 5 - Δ 4 ; 3/3-OH — 3 - C = 0
R E F .
S-849
T-1030
T-1030
T-1030
T-1030
T-1030
T-1034
T-1032
T-1032
T-1032
T-1032
T-1032
T-1034
T-1034
T-1032; T-1034
T-1030; T-1031; T-1032; T-1034
TABLE I I I
T r a n s f o r m a t i o n s by Genus : PROACTINOMYCES
545
SPECIES
erythropol is
globerulus
minimus
paraffinae
polychromogenes
1 r e s t r i c t u s
roseus
rubroper t inc tus
species
SOURCE
NG
NG
NG
NG
NG
NG
NG
NG
NG
SUBSTRATE
5-cholesten-3/3-ol (sole carbon source)
5-cholesten-3/3-ol aceta te
4-choles ten-3-one
5-st igmasten-3/3-ol
5 ,22-s t igmastadien-3/3-ol
5-cholesten-3j3-ol (sole carbon source)
5 -cholesten -3/3-ol (sole carbon source)
5-cholesten-3/3-ol (sole carbon source)
5-cholesten-3/3-oi (sole carbon source)
5-cholesten-3/3-01 (sole carbon source)
5-cholesten-3/3-ol (sole carbon source)
5 -cholesten -3/3-ol (sole carbon source)
l , 3 ,5 (10) -es t r a t r i ene -3 ,17 /3 -d io l (ail subs t ra tes-Ref . T-1033) (sole carbon source)
3 -hydroxy-1 ,3 , 5 (10) -es t ra t r i en-17-one
3a -hydr oxy -5a -andr ostan -17 -one
3ß-hydr oxy- 5-androsten -17-one
4 -p regnene-3 ,20-d ione
3a, la, 12a-tr ihydroxy-5/3-cholanic acid
3/3-hydroxy-5-cholenic acid
REACTION
utilization
-choiestenone —» r ing A cleavage
17j3-CH(CH3) CH2CH2CH2CH ( C H 3 ) 2 - 17/3-COOH
3/3-OH-3-C = 0 ; Δ 5 - Δ 4
3/3-OH-3-C = 0 ; Δ 5 - Δ 4
utilization
util ization
util ization
utilization
utilization
7ξ-ΟΗ
Δ 5 - Δ 4 ; 3 / 3 - Ο Η -3-C = 0
utilization
utilization
utilization
utilization
utilization
util ization
util ization
utilization
R E F .
T-1030; T-1031
T-1032
T-1034
T-1034
T-1032
T-1032
T-1030
T-1030
T-1030
T-1030
T-1030
K-474; K-475
K-474; K-475
T-1030
T-1033
T-1033
T-1033
T-1033
T-1033
T-1033
T-1033
546
TABLE I I I
TAXONOMY
T r a n s f o r m a t i o n s by Genus : PROACTINOMYCES PROTAMINOBACTER (Schizo. - Pseudomonadales)
SPECIES
species
PROTAMINOBACTER
alboflavum (alboflavus)
SOURCE
NG
ATCC-8458
SUBSTRATE
choles tan-3a-o l
cholestan-3/3-01
5/3-cholestan-3a-ol
5/3-cholestan-3/3-ol
5/3-cholestan-3/3-ol aceta te
5a, 6ß-dibromocholestan -3/3-ol
3ß-chloro-5-choles tene
5-cholesten-3/3-ol
5-choiesten-3/3-01 aceta te
d ichoies teryl e ther
4-choies ten-3-one
24/3-methyl -5 ,7 ,22-choles ta t r ien-3/3-01
5-stigmasten-3/3-ol
5,22-st igmastadien-3/3-01
e s t r an -3 -one
5α - andr ostan - 3 - one
17a-hydr oxy - 5a-andr ostan - 3 - one
5a-andros tane-3 ,17-d ione
5/3-androstane-3,17-dione
17/3-hydroxy-4-estren-3-one
4 -andros tene-3 ,17-d ione
4 ,6 -andros tad iene -3 ,17-d ione
5a-pregnan-3-one
5/3-pregnan-3-one
l l /3-hydroxy-5/3-pregnan-3-one
14a-hydroxy-5/3-pregnan-3-one
17a-hydroxy-5/3-pregnan-3-one
20-hydroxy-5/3-pregnan-3-one
REACTION
utilization
utilization
utilization
utilization
utilization
-
-
Δ - Δ ;3/3-OH^ 3 - C = 0
utilization
utilization
util ization
utilization
utilization
utilization
S 4 Δ ; enol.
1,4
Δ
Δ 1 ' 4
1 4
Δ ' 1 4
Δ ' 1
Δ ; enol. 1
Δ 1
Δ 1 4
Δ ' 1 4
Δ '
Λ 1 ' 4
1 4
Δ '
Λ 1 ' 1
1 4
Δ '
R E F .
T-1033
T-1033
T-1033
T-1033
T-1033
T-1033
T-1033
H-406; H-407
T-1033
T-1033
T-1033
T-1033
T-1033
T-1033
S-866
S-866
S-866
S-866
S-866
S-863
S-863
S-863
S-866
S-866
S-866
S-866
S-866
S-866
TABLE I I I
Transformat ions by Genus: PROTAMINOBACTER
547
SPECIES
alboflavum (aiboflavus)
SOURCE
ATCC-8458
SUBSTRATE
5a-pregnane-3 ,11-d ione
5a-pregnane-3 ,20-d ione
11/3-hydroxy-5/3-pregnane-3,20-dione
14a -hydroxy-5/3-pregnane - 3 , 2 0 -dione
17a-hydroxy-5/3-pregnane-3,20-dione
21 -hydroxy -5/3-pr egnane -3 ,20 -dione
21 -hydroxy-δξ -p regnane -3 ,20 -dione
1 I ß , 21 -dihydroxy -5/3 -pregnane -3,20-dione
11/3,21 -dihydroxy -5ξ -pregnane -3 ,20-dione
11/3,17«, 21- t r ihydroxy-5/3-preg-nane-3 ,20-d ione
11/3,14a, 17a, 21-tetrahydroxy-5/3-pr egnane-3 ,20-dione
5a -p regnane -3 ,11 ,20 - t r i one
17a, 21 -dihydroxy -5/3 -pr egnane -3 ,11 ,20 - t r ione
17a -hydroxy-4 -p regnene-3 ,20-dione
11/3,17a -dihydroxy -4 -pregnene -3,20-dione
17a, 21-dihydroxy-4-pr egnene -3,20-dione
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
9a- f luoro- l l /3 ,17a , 21-tr ihydroxy-4 -p regnene-3 ,20-d ione
16/3-fluoro-l l /3,17a,21-tr ihydroxy-4-pregnene-3 ,20-d ione
11/3,14a, 17a, 21 - te t rahydroxy - 4 -pregnene-3 ,20-d ione
REACTION
1 4
Δ
Δ ' l 1
Δ
A ' ' '
L 1
Δ '
Δ 1 ' 4
•1
Δ
1 4
Δ '
Δ
A 1 '*
A'«*
Δ 1 ' 1
1 , 4
Δ '
l
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
R E F .
S-866
S-866
S-866
S-866
S-866
S-866
S-863; S-866
S-866
S-866
S-866
S-866
S-866
S-866
S-863
S-863
S-863
S-863
S-863
B-51
S-863
548
TABLE I I I
Transformations by Genus: PROTAMINOBACTER
SPECIES
alboflavum (alboflavus)
rub rum
SOURCE
ATCC-8458
NRRL
ATCC-8457
SUBSTRATE
17a,21-dihydroxy-14a, 15a-oxido-4-pregnene-3 ,20-d ione
11/3 ,17a,21- t r ihydroxy-14a,15a-oxido-4-pregnene-3 ,20-dione
4 - p r e g n e n e - 3 , 1 1 , 20- t r ione
17a, 21 -dihydroxy -4-pregnene -3 , 1 1 , 2 0 - t r ione
2a-f luoro-17a, 21-dihydroxy-4-pregnene - 3 , 1 1 , 2 0 - tr ione
14a, 17a, 21 - t r ihydroxy-4 -p reg -nene -3 ,11 ,20 - t r i one
4 ,16-pregnad iene-3 ,20-d ione
17a,21-dihydroxy-4,9(11) -
17a, 21-d ihydroxy-4 ,14-pregna-diene-3 ,20-dione
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
e s t r an -3 -one
5a-andros tan-3-one
17a-hydroxy-5a-andros tan-3-one
5a-andros tane-3 ,17-d ione
5/3-androstane-3,17-dione
17/3-hydroxy-4-estren-3-one
4 -andros tene-3 ,17-d ione
4 ,6 -andros tad iene -3 ,17-d ione
5a-pregnan-3-one
5ß-pregnan-3-one
l l /3-hydroxy-5/3-pregnan-3-one
14a-hydroxy-5/3-pregnan-3-one
17a-hydroxy-5/3-pregnan-3-one
20-hydroxy-5ß-pregnan-3-one
5a-pregnane-3 ,11-d ione
REACTION
Δ
Δ
Δ
Δ
Δ
Δ
Δ
Δ
Δ
-
-
-1 4
Δ ' ; enol.
A ' ' 4
Δ 1>4
Δ 1 4
Δ 1
Δ ; enol. 1
Δ 1
Δ 1 4
Δ 1 ,4
Δ
Λ 1 ' 4
1 4
Δ '
Λ 1 ' 1
Λ 1 ' 4
Λ 1 ' 4
R E F .
S-863
S-863
S-863
S-863
H-401
S-863
S-863
S-863
S-863
M-587
M-587
M-587
S-866
S-866
S-866
S-866
S-866
S-863
S-863
S-863
S-866
S-866
S-866
S-866
S-866
S-866
S-866
pregnadiene-3, 20-dione
T A B L E I I I
Transformations by Genus: PROTAMINOBACTER
549
SPECIES
rubrum
SOURCE
ATCC-8457
SUBSTRATE
5a-pregnane-3 ,20-d ione
l l /3-hydroxy-5/3-pregnane-3, 20-dione
14a-hydroxy-5/3-pregnane-3,20-dione
17a -hydr oxy - 5/3 -pr egnane - 3 , 2 0 -dione
21-hydroxy-5/3-pregnane-3,20-dione
21 -hydroxy-5ξ -p regnane -3 ,20 -dione
11/3, 21 -dihydroxy - 5/3-pregnane -3,20-dione
l l /3 ,21-d ihydroxy-54-pregnane-3,20-dione
l l /3 ,17a ,21- t r ihydroxy-5/3-preg-nane-3 ,20-d ione
11/3,14a, 17a ,21- te t rahydroxy-5/3-pregnane-3,20-dione
5a -p regnane -3 ,11 ,20 - t r ione
17a, 21-dihydroxy-5/3-pregnane -3 , 1 1 , 20- t r ione
17a-hydroxy-4-p regnene-3 ,20-dione
11/3,17a-dihydroxy-4-pregnene -3,20-dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
11/3,17a, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
11/3,14a, 17a, 21 - t e t r ahydroxy-4-pregnene-3 ,20-d ione
17a, 21-dihydroxy-14a, 15a-oxido-4-pregnene-3 ,20-d ione
11/3,17a, 21- t r ihydroxy-14a , 15a-ox ido-4-pregnene-3 ,20-d ione
4 - p r e g n e n e - 3 , 1 1 , 20- t r ione
17a ,21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r i one
REACTION
1 1
Δ ' 1 , 4
Δ
1 4
Δ '
J 4
Δ '
Λ 1 ' 4
Δ
1 4
Δ
4
Δ
Λ 1 ' 4
1 4
Δ
1 , 4
Δ 1 4
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
Δ1
R E F .
S-866
S-866
S-866
S-866
S-866
S-863; S-866
S-866
S-866
S-866
S-866
S-866
S-866
S-863
S-863
S-863
S-863
S-863
S-863
S-863
S-863
S-863
S-863
550
TABLE I I I
T r a n s f o r m a t i o n s by Genus: PROTAMINOBACTER PROTEUS
PSEUDOMONAS
TAXONOMY
(.Schizo. - Eubacter ia les) iSchizo. - Pseudomonadiales)
SPECIES
rubrum
PROTEUS
spec ies
PSEUDOMONAS
aeruginosa
(in mixed cul ture with Mycococcus sp. Ax )
aureofaciens
azoformicans
SOURCE
ATCC-8457
r a t caecum
IAM (HX-19)
NG
IAM (MT)
IAM (Baltimore)
IFO (3505)
IAM
IAM
NG
IAM
IAM
NRRL B-1543
IAM
SUBSTRATE
14a ,17a ,21 - t r i hydroxy-4 -p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
17a ,21-dihydroxy-4 ,9(11)-pregnadiene-3 ,20-d ione
17a ,21-d ihydroxy-4 ,14-pregnadiene-3 ,20-d ione
4 ,16-pregnad iene-3 ,20-d ione
3a, 7a, 12a-tr ihydroxy-5/3-cholanic acid
17a, 21-dihydroxy-4-pregnene -3, 20-dione
5-cholesten-3/3-01 (sole carbon source)
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
11/3 ,17a,21- t r ihydroxy-4-p regnene -3 , 20-dione
4-pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
5-cholesten-3/3-01 (sole carbon source)
4 -pregnene-3 ,20-d ione
17a, 21-dihydroxy - 4 -pregnene-3,20-dione
4-pregnene-3 ,20-d ione
REACTION
Δ1
1
Δ
Δ1
Δ 1
11/3-OH
utilization
Δ1
oxidation
utilization
oxidation
R E F .
S-863
S-863
S-863
S-863
N-675
S-849
T-1030
S-849
S-849
1-428
1-428
1-414; 1-415
1-414; 1-415
T-1030
1-414; 1-415
1-414; 1-415
S-849
1-414; 1-415
TABLE I I I
Transformat ions by Genus: PSEUDOMONAS
551
SPECIES
azoi 'ormicans
boreopolis
i r rad ia ted mutant
caudata
chlororaphis
SOURCE
IAM
ATCC-13476
IAM
IAM
Take da (109)
Takeda (109)
IAM
IAM
IAM (1511)
SUBSTRATE
17ö,21-d ihydroxy-4-pregnene-3,20-dione
17o , ,21-dihydroxy-4-pregnene-3,20-dione
4-pregnene-3 ,20-dione
17a ,21-d ihydroxy-4-pregnene-3,2C-dione
4 -p regnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
3a-hydroxy-5a-andros tan-17-one
3ß-hydroxy-5-andros ten-17-one
17/3-hydr oxy -4 -andros ten -3 -one
l , 4 - and ros t ad i ene -3 ,17 -d ione
4 -pregnene-3 ,20-d ione
17a-hydroxy-4-pregnene-3 , 20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
l l ß , 2 1 - d i h y d r o x y - 4 - p r e g n e n e -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
REACTION
Δ]
Δ1; 20-C = O -20/3-OH
11/3-OH
Δ1; 20-C = O -20/3 -OH
11/3-OK
Δ1; 11/3-OH
Δ ' ; 17 /3-OH-1 7 - C = 0
17/3-OH — 1 7 - C - O
Δ1; 17G-OH-17j3-(20-C=O-21-OH) - 1 7 a -oxa-17-C = 0
Δ1
R E F .
1-414; 1-415
T-96C
T-960
T-96C
1-414; 1-415
1-414; 1-415
N-652
N-652
T-961
1-414; 1-415
1-414; 1-415
N-648
N-648
N-648
N-648
N-648
N-648
N-648
N-648
N-648
N-648
N-648
552
TABLE I I I
Transformat ions by Genus: PSEUDOMONAS
SPECIES
chlororaphis
cohaerens
cruciviae
dacunhae
SOURCE
IAM (1511)
IAM
ATCC-13262
IAM
ATCC-13261
IAM (A-6-3)
SUBSTRATE
17a ,21-d ihydroxy-4-pregnene-3,20-dione
l l ß , 1 7 a , 2 1 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
15a ,17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - l , 4 -pr egnadiene -3 ,20 -dione
4 -pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4 -andros tene-3 ,17-d ione
19-hydroxy-4 -andros tene -3 ,17-dione
4-pregnene-3 ,20-d ione
17a, 21-dihydroxy-4-pr egnene-3,20-dione
4 -andros tene-3 ,17-d ione
19-hydroxy-4 -andros tene -3 ,17-dione
21-hydroxy-4-p regnene-3 ,20-dione
1 Iß , 21 -dihydr oxy -4 -pr egnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
REACTION
17a-OH-17/3-(20-C=0-21-OH) — 1 7 - C = 0
Δ1
17α-ΟΗ-17]3-(20-C = 0-21-OH) -17-C = 0
Δ1; 17α-ΟΗ-17/3-(20-C = O-21-OH) - 1 7 - C = 0
17a-OH-17/3-(20-C=0-21-OH) — 1 7 - C = 0
17α-ΟΗ-17β-(20-C = 0 - 2 1 - O H H 1 7 - C = 0
oxidation
-
1
9α-ΟΗ; Δ ; r ev . aldol. , enol.
1
Δ ; rev . aldol. (Formaldehyde Î ) enol„
oxidation
1
Δ
1
Δ
Δ1; r ev . aldol. (Formaldehyde! ) enol.
1
Δ
1
Δ
1
Δ
R E F .
N-648
N-648
N-648
N-648
N-648
N-648
1-414; 1-415
1-414; 1-415
M-597
M-597
1-414; 1-415
1-414; 1-415; S-849
M-597
M-597
S-848
S-848
S-848; S-849
TABLE I I I
553
T r a n s f o r m a t i o n s by G e n u s : PSEUDOMONAS
SPECIES
dacunhae
desmolyt ica
docunhae (probably dacunhae)
f luorescens
(in mixed cul ture with Mycococcus sp. A J
(in mixed cul ture with Mycococcus sp. AJ
SOURCE
LAM(A-6-3)
IAM (G-1-7) (G-1-13) (R-lC-2)
S
IAM
IAM
ATCC-13475
IAM (A-3-8)
IAM(A-3-12)
IAM
SUBSTRATE
l l ß , 17α, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
1 Ία, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
4 -p regnene -3 , 20-dione
17a-hydroxy-4-pregnene-3,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
l l /3 ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3 ,11 ,20- t r ione
4 -p regnene-3 ,20-d ione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
4 -p regnene-3 ,20-d ione
17a, 21 -dihydroxy-4-pregnene -3 ,20-dione
REACTION
-
-
1
Δ
-
-
1
Δ
1
Δ
Δ1
-
-
oxidation
-
oxidation
-
1 2 0 - C = O ^ k
20/3-OH
-
1
Δ
oxidation
R E F .
S-848
S-848
S-849
S-859
S-859
S-849
S-849
S-849; S-859
S-849
S-849
1-414; 1-415
1-414; 1-415
1-414; 1-415
1-414; 1-415
T-960; U-1039
S-849
S-849
1-414; 1-415
1-414; 1-415
SPECIES
f luorescens
(in mixed cul ture with Mycococcus sp. Ax)
fragi
(in mixed cul ture with Mycococcus sp. Ax)
gaeger i
gelidicola
graveoiens
(in mixed cul ture with Mycococcus sp. Ax)
indoloxidans
SOURCE
IFO(3081)
IFO (3459)
NG
NRRL
Takeda (M-8)
IFO (3458)
IAM
IAM
IFO (3460)
NRRL
NRRL
SUBSTRATE
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
11/3,17a, 21- t r ihydroxy-4-pr eg -nene-3 ,20-d ione
5-choles ten-3ß-ol
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
17a, 21-d ihydroxy-4-pregnene-3,20-dione
11/3,17a, 21 - t r ihydroxy -4 - p r eg -nene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
4 -pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
11/3,17a, 21 - t r ihydroxy - 4 -pregnene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
REACTION
-
-
1
Δ
-
-
-
-
2 0 - C = O ^ 20/3 -OH
-
1
Δ
oxidation
oxidation
oxidation
-
1
Δ
-
-
-
-
-
—
R E F .
S-849
S-849
1-428
1-428
T-1030
M-587
M-587
M-587
N-652
1-428
1-428
1-414; 1-415
1-414; 1-415
1-414; 1-415
1-414; 1-415; S-849
1-428
1-428
M-587
M-587
M-587
M-587
M-587
M-587
T r a n s f o r m a t i o n s by Genus: PSEUDOMONAS
TABLE I I I
554
TABLE I I I
Transformat ions by Genus: PSEUDOMONAS
555
SPECIES
iner t ia
j aeger i
lacunogenes
melanogenes
myxogenes
n i t roreductans
ochracea
oleovorans
SOURCE
IAM
IAM(AHH-23) (AHH-27) (AHH-28)
r a t fèces
IAM
IAM
IAM
IAM
IAM
ATCC-13474
Takeda (SP-125)
SUBSTRATE
4-pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3, 20-dione
5-cholesten-3j3-ol
4 -p regnene-3 ,20-d ione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3, 20-dione
4 -pregnene-3 ,20-d ione
17a, 21-dihydr oxy-4-p regnene-3,20-dione
4 -pregnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
4 -p regnene-3 ,20-d ione
17a, 21-dihydr oxy-4-pregnene -3,20-dione
17a, 21-dihydr oxy-4 -p regnene-3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
REACTION
oxidation
-
-
util ization
oxidation
-
-
-
-
-
oxidation
-
-
-
1
Δ
Δ1; 11/3-ΟΗ
Δ1; 20-C = O -20/3-OH
Δ1
R E F .
1-414; 1-415
1-414; 1-415
S-849
W-1067
1-414; 1-415
1-414; 1-415
1-414; 1-415
1-414; 1-415
1-414; 1-415
1-414; 1-415
1-414; 1-415
1-414; 1-415
1-414; 1-415
1-414; 1-415
T-960
T-960
T-960
Ν-652
TABLE I I I
T r a n s f o r m a t i o n s by Genus : PSEUDOMONAS
SPECIES
ovalis
*
pavonacea
per lu r ida
p ic torum
putida
pyocyanea
rathonis
riboflavinus
SOURCE
IAM(A-10-3; C 3 - 3 ; S-5)
IAM
NRRL
IAM
IAM
NG
IAM
NRRL
ra t cecum
IAM
IAM
SUBSTRATE
17a, 21 -dihydroxy-4-pregnene -3,20-dione
4-pregnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene-3,20-dione
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
4-pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
4-pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
5-cholesten-3/3-ol
4 -pregnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
3a, 7a, 12a- t r ihydroxy-5ß-choianic acid
4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
4-pregnene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
REACTION
-
oxidation
1
Δ
-
-
-
oxidation
-
-
-
-
-
-
—
-
—
oxidation
1
Δ
oxidation
R E F .
S-849
1-414, 1-415
I 414; 1-415
M-587
M-587
M-587
1-414; 1-415
I 414; 1-415
1-414; 1-415
1-414; 1-415
T-1030
1-414; 1-415
1-414; 1-415
M-587
M-587
M-587
N-675
1-414; 1-415
1-414; 1-415
1-414; 1-415
1-414; 1-415; S-849
556
TABLE I I I
T r a n s f o r m a t i o n s by Genus : PSEUDOMONAS
557
SPECIES
roseum
schuylkill
schuylkil i iensis
species
(later - t e s tos t e ron i , ATCC-11966 - Ref. M-560)
SOURCE
IAM
IAM(CB-6; B-6)
IAM
ATCC-13261
ATCC-13262
ATCC-13263
3en May Lab Chicago
SUBSTRATE
4 -p regnene -3 ,20 -d ione
17a ,21-d ihydroxy-4-pregnene-3, 20-dione
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
4-pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -p regnene -3,20-dione
4 -andros tene-3 ,17-d ione
4 -andros t ene -3 ,17 -dione
4 -andros tene-3 ,17-d ione
19-hydroxy-4-andros tene -3,17-dione
1,3, 5(10)-es t ra t r iene-3,17/3-diol (all s u b s t r a t e s , this re fe rence using tes tos te rone adapted cells)
3 -hydroxy-1 ,3 , 5 (10) -es t ra t r i en-17-one
5a -andros tane-3 ,17-d ione
3a -hydroxy-5a -androstan-17 -one
3/3 - hydroxy - 5 -androsten -17 -one
3a-hydroxy-5-androsten -17-one
17a-hydroxy-4-andros ten-3-one
17/3-hydroxy-4-androsten-3-one (soie carbon source)
17/3-hydroxy-17a-methyl-4-andros ten-3-one
REACTION
oxidation
-
-
oxidation
-
Δ
9α-ΟΗ; Δ ; rev . aldol; enol.
7/3-OH
11a-OH
1
9a-OH; Δ ; rev. aldol. ; enol.
9a-OH; Δ1; rev. aldol; enol. ; 17-C = 0 -17/3-OH
1
Δ ; rev . aldol; (Formaldehyde Î ); enol.
-
oxidation
oxidation
oxidation
oxidation
oxidation
17/3-OH -*17-C=0
—
R E F .
1-414; 1-415
1-414; 1-415
S-849
1-414; 1-415
1-414; 1-415
D-171
D-171
D-171; M-597
D-171; M-597
D-171; M-597
D-171; M-597
D-171; M-597
T-968
T-968
T-968
T-968
T-968
T-968
T-968
T-968
T-968
558
TABLE I I I
T r a n s f o r m a t i o n s by Genus : PSEUDOMONAS
SPECIES
species (later - t e s tos te ron i , ATCC-11966 - Ret. M-560)
SOURCE
Ben May Lao Chicago
C
IAM
NG
Searle
Takeda (109)
SUBSTRATE
4-andros teae-3 ,17-d io . ie
21-hydroxy-4-pregnene-3 ,20-dione
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-dione
17a,21 -d ihydroxy-4-pregneie -3? 11 ,20- t r ione
3a-hydroxy- 5a-androstan -17-o;ie
17α, 21 -dihydroxy -4 -pr egnene -3,20-dione
1,3, 5( lC)-es t ra t r iene-3 ,17/3-dioi
subs t r a t e s - T-1C33, S-786, S-787)
3 - h y d r o x y - l , 3 , 5 ( 1 0 ) - e s t r a t r i e n -17-one
3a - hydroxy - 5a - androstan -17 - one
3/3- hy dr oxy - 5 -andr osten -17 -one
17/3-hydroxy-4-androsten-3-one
4-pregne ie -3 ,20-d ione
3a, 7a, 12a-trihydroxy-5/3-cholanic acid
3-hydroxy-5-cholenic acid
5 ,6-dibromo-choiestane-3/3-oi acetate
3/3-chloro-5-cholesteie
24/3-methyl-5, 7,22 -cho lesta -trien-3/3-oi
4 -andros tene-3 ,17-d ione
19-hydroxy-4-andros tene -3 ,17-dione
17a,21 -d ihydroxy-4-pregnene-3,20-dione
REACTION
oxidation
-
-
d, l -3a-OH — d-3 - C = 0 + l -3a-OH
-
-
utilization
utilization
utilization
utilization
utilization
utilization
-
-
utilization
9α-ΟΗ; Δ*; rev . aldoi. ; enol.
Δ ; rev . aldol. (Formaldehyde Î ); enol.
l l ß - O H
R E F .
T-968
T-968
T-968
T-968
W-1102
S-849
T-1033
T-1033
T-1033
T-1033
S-786; S-787
S-787; T-1033
T-1033
T-1033
T-1033
T-1033
T-1033
D-169
D-169
N-652; U-1038
( , s ü ie c a r D on s o u r ce - a l l
TABLE I I I
T ransformat ions by Genus: PSEUDOMONAS
559
SPECIES
species
1 (in mixed cul ture with one of the following: Mycococcus sp . Alt
1 A-io> A14, A15, A18, A ^ , 1 A A A A A
A32
s t r iafac iens
1 vin mixed cul ture with Mycococcus sp. A,)
s tu tze r i
1 synxantha
1 tae t ro lens
SOURCE
Takeda (109)
(109-mutant)
(M-8)
(125)
(B- l )
IFO (3309)
IAM
IAM
IAM
SUBSTRATE
17ß,21-d ihydroxy-4-pregnene-3,20-dione
1 la, 21 -dihy droxy -4 -pr egnene -3,20-dione
17«, 21-d ihydroxy-4-pregnene-3,20-dione
11/3,17o,21-tr ihydroxy-4 p r e g -nene-3 ,20-d ione
4 -p regnene -3 ,20 -dione
17a, 21-dihydroxy-4-pr egnene-3,20-dione
4-pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4-pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
REACTION
Δ ' ; 2 0 - C - O -20/3 -OH
Δ ' ; 20-C=O 2G/3-OH
Δ1; 11/3-OH
Δ ' ; 2 0 - C - O — 20/3-OH .
Δ'
Δ ' ; 20-C=O -» 2C/3-OH
1
Δ
—
—
oxidation
-
-
-
-
R E F .
U-1038
U-1040
T-961; U-1040
N-652; y_il_03?
N-652; U-1Ü39
U-1039
U-1039
1-428
1-428
1-428
1-414; 1-415
1-414; 1-415
1-414; 1-415
1-414; 1-415
1-414; 1-415
1-414; 1-415
1
Δ
560
TABLE I I I
Transformat ions by Genus: PSEUDOMONAS
SPECIES
tes tos te roni
SOURCE
ATCC-11996
SUBSTRATE
Type Reaction for j3-hydroxy s tero id dehydrogenase
3/3 -hydroxy -5 -andr osten -17 -one + D P N + ^ 4 - a n d r o s t e n e - 3 , 17-dione + DPNH + H+
17/3-hydroxy-4-androsten-3-one + DPN+ ^ 4 - a n d r o s t e n e - 3 , 17-dione + DPNH + H+
(see r e f e rences for isolat ion, purif ication, specifici ty, kinet ics and inhibition of enzymeSo )
Type Reaction for 3a-hydroxy s tero id dehydrogenase
3a -hydroxy - 5a -androstan -17 -one + DPN ^ a n d r o s t a n e - 3 , 1 7 -dione + DPNH + H+
(see r e f e rences for isolat ion, purif icat ion, specifici ty, kinet ics and inhibition of enzymes . )
Type Reaction for A 5 -3-ke to -s te ro id i s o m e r a s e
5 -andros tene -3 ,17-d ione-* 4 -andros tene-3 ,17-d ione
(see r e f e rences for isolation purif ication, specifici ty, kinet ics and inhibition of enzymes . )
Ring A dehydrogenation
Δ1 -dehydrogenase
Δ4 -5α-dehydrogenase
Δ4 - 5/3 -dehydrogenase
(see r e f e rences for isolat ion, purif icat ion, specifici ty, kinet ics and inhibition of enzymes and Ref. T-1005 for compar ison with "s te ro id r ing dehydrogenase" from No card ia . )
3α-hydroxy - 5α-androstan -17-one
5a -andros t ane -3 ,17 -d ione -(cell free ex t r ac t s - Ref. L-507)
REACTION
3 / 3 - O H - 3 - C = 0 ; 17 /3-OH-1 7 - C = 0
3 a - O H - * 3 - C = 0
Δ 5 -+Δ 4
Δ ^ Δ 4
3a-OH— 3 - C = 0
Δ1
Δ 1 ' 4
R E F .
D-155; F-241; F-242; M-559; M-560; T-964; T-965; T-966; T-967; T-969
D-155; M-560; R-767; T-964; T-965; T-971
K-43T, K-438; T-583; T-964; T-972; W-1064
L-507; L-508; L-509; T-1005
D-155
L-507; L-508; L-509
L-507; L-508
1
TABLE I I I
Transformat ions by Genus: PSEUDOMONAS
561
SPECIES SOURCE SUBSTRATE REACTION R E F .
t es tos te ron i ATCC-11996 5o-andros tane-3 ,17-d ione (cell free ex t rac t s - Ref„ L-507)
17/3-hydroxy-5/3-androstan-3-one
L-508
L-507
A-nor -17/3 -hydroxy-3 -andr osten-2-one
17/3-hydroxy-5a-est ran-3-one
17ß-hydroxy-4-es t ren-3-one
5 -androstene -3j8,17/3-diol
1 la- methyl -5 -andros tene -3/3,17/3-diol
17/3-hydroxy-4-androsten-3-one
11/3,17/3-dihydr oxy-4-andr osten -3-one
3/3-hydroxy-5-androsten-17-one
1 -andr ostene -3 ,17 -dione
4 -andros tene -3 ,17-d ione
17/3-OH-17-C = 0
Δ1*4
17|3-OH-47-C = 0 ; Δ4
9a-OH; 17/3-OH ->17-C = 0
Δ*; 17/3-OH-» 17-C = 0
Δ1; enol. 17/3-OH—17-C=0
Δ ; enol.
Δ 5 - Δ 4 ; 3 / 3 - Ο Η -3-C = 0 ; 17/3-OH - 1 7 - C = 0
Δ5—Δ4; 3/3-OH-3-C = 0
Δ1
17/3-OH-17-C = 0 ; Δ 1
17/3-OH-17-C=0
1 7 / 3 - O H - 1 7 - 0 0
Δ 5 - Δ 4 ; 3 / 3 - Ο Η -3-C = 0
Δ 5 - Δ 4 ; 3 / 3 - Ο Η -3-C = 0 ; 1 7 - C = 0 -17/3-OH
Δ4; 17-C = 0 -17/3-OH
Δ1; 17-C = 0 -17/3-OH
Δ 1
1 7 - C = 0 — 17/3-OH
L-508
L-508
S-885
L-508
L-507; L-508; L-509
L-508
T-966
T-966
L-507
L-507
D-155; L-508; T-966
T-966
T-966
T-966
L-508
L-508
L-507; L-508
T-966
1
Δ
1
Δ
562
TABLE I I I
T r a n s f o r m a t i o n s by Genus: TAXONOMY
PSEUDOMONAS PSEUDOMYCODERMA (Imperf. - Moniliales)
PSILOCYBE (ßasidio0 - Agaricales)
SPECIES
tes tos teroni
tr ifoli i
xanthe
PSEUDOMYCODERMA
miso
PSILOCYBE
caeru lescens (var. mazatecorum)
SOURCE
ATCC-11996
IAM
IAM
FRI
S i
SUBSTRATE
17/3-hydroxy-17a-methyl-4-andros ten-3-one
5 a - l - e s t r e n e - 3 , 1 7 - d i o n e
4 - e s t r ene -3 ,17 -d ione
l ,3 ,5 (10) -es t r a t r i ene -3 ,17 i3 -d io l
3 - h y d r o x y - l , 3 , 5 ( 1 0 ) - e s t r a t r i e n -17-one
21-hydroxy-4 -p regnene-3 ,20-dione
(use of inhibi tors to in-c r e a s e 9α-OH)
4-pregnene-3 ,20-d ione
11/3,17«, 21- t r ihydroxy-4-preg-nene-3 ,20-d ione (use of dr ied cells)
3/3-hydroxy-5-pregnen-20-one
4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -p regnene -3,20-dione
4 -pregnene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
3/3 -hydroxy - 5 -pregnen -20 -one
4 -pregnene-3 ,20-d ione
REACTION
Δ1
4
Δ ; enol0
1
Δ ; enol.
17/3-OH—17-c=o 1 7 - C = 0 ^ 1 7 / 3 -OH
9a-OH
9a-OH
9a-OH
Δ1
Δ -»Δ ; 3/3-OH-3 - C = 0
-
-
-
-
-
3/3-OH-3-C = 0 ; Δ5-»Δ4;11α-ΟΗ
3 ß - O H ^ 3 - C = 0 ; Δ 5 - Δ 4 ; 1 1 α - Ο Η ; 21-OH; l i a , 2 1 -diOH l l a - O H
l l a -OH;21-OH; l l a , 2 1 - d i O H
R E F .
L-508 1
L-508
L-508; L-509
D-155; T-966
T-966
P-740
S-898
S-885
F-231
T-966
1-414; 1-415
1-414; 1-415
1-414; 1-415
1-414; 1-415
S-849
C-113
C-113
C-113
C-113
TABLE I I I
T ransformat ions by Genus: PSILOCYBE
563
SPECIES
cae ru lescens * (var. mazatecorum)
caeru l ipes
mexicana *
semperviva
SOURCE
SY
AL (C-236)
SY
UB
UB
SUBSTRATE
17a, 21 -d ihydroxy-4-pregnene -3,20-dione
4 -p regnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4 -andros tene -3 ,17-d ione
4 -p regnene-3 ,20-d ione
14/3-hydroxy-3 -keto-5j3 -20(22) -cardenolide
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide
3/3, 5/3,14j3-trihydroxy-19-oxo-20(22)-cardenolide
3/3,l la,14/3-trihydroxy-5/3-20(22)-cardenolide
3/3,14/3,16/3-trihydroxy-5/3-20(22)-cardenolide
3/3, 5/3,14/3,19-tetrahydroxy-20(22)-cardenolide
21 -hydroxy-4 -p regnene -3 ,20 -dione
14/3-hydroxy-3-keto-5/3-20(22)-cardenolide
REACTION
l i a - O H
oxidation -products not identified
l i a - O H
oxidation -products not identified
oxidation -products not identified
7/3-OH
3/3-OH -> 3-C = 0
7/3-OH; 3/3-OH - 3 - C = 0
7/3-OH
12/3-OH
oxidation -products not identified
oxidation -products not identified
oxidation -products not identified
oxidation -products not identified
oxidation -products not identified
3 -C=0-3 /3 -OH
12/3-OH; 3-C = 0 —3/3-OH
R E F .
C-113
S-825
C-113
W-1075
W-1075
W-1075
W-1075
W-1075
W-1075
W-1075
W-1075
W-1075
W-1075
W-1075
W-1075
W-1075
W-1075
564
Transformat ions by Genus:
TABLE I I I
PSILOCYBE PULLULARIA
PYCNODOTHIS
TAXONOMY
(Imperf. - Moniliales) (Imperf. - Sphaeropsidales)
SPECIES
semperviva
PULLULARIA
pullulans
species
PYCNODOTHIS
species
SOURCE
UB
FRI
NG (Sandoz)
NRRL
ATCC-11721
SUBSTRATE
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide
3/3,11a, 14/3-trihydroxy-5/3-20(22)-cardenolide
3/3,14/3,16j3-trihydroxy-5j3-20(22)-cardenolide
3/3, 5/3,14/3-trihydroxy-19-oxo-20(22)-cardenolide
17a ,21-d ihydroxy-4-pregnene-3,20-dione
3/3,6/3, 8/3,14/3-tetrahydroxy-4, 20,22-bufatr ienolide 6-aceta te 3-glucoside
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide 3-[glucosyl-digitoxosy 1 - digitoxosy 1 -digitoxoside]
Digilanid - A
plant saponins
4 -andros tene-3 ,17-d ione
4-pregnene-3 ,20-d ione
21-hydroxy-4-p regnene-3 ,20-dione
REACTION
12/3-OH
oxidation -products not identified
oxidation -products not identified
1 9 - C = 0 - > 19-OH
-
3β-[1χξ -gluco-side] — 3/3-OH
-hydrolysis of glycosides to aglycones (sapogenins)
1
Δ
17/3-AC-17-c=o Δ ; 17/3-Ac -» 1 7 - C = 0
Δ1; 17/3-Ac — 17/3-OH
17/3-(20-C=O-21-OH) -> , 1 7 - C = 0 ; Δ
R E F .
W-1075
W-1075
W-1075
W-1075
S-849
S-936a
S-936a
S-936a
K-478
K-450
K-450
K-450
K-450
K-450
565
TABLE I I I TAXONOMY
Transformat ions by Genus: PYCNODOTHIS PYCNOSPORIUM PYRENOPHORA PYRONEMA PYTHIUM
(Imperf. - Sphaeropsidales) vAsco. - Sphaeriales) (Asco. - Pezizales) (Phyco. - Peronosporaies)
SPECIES
species
PYCNOSPORIUM
species
PYRENOPHORA
greminea
t e r e s
PYRONEMA
confluens
PYTHIUM
ultimum
SOURCE
ATCC-11721
ATCC-12231 (QM-703)
FRI
NIHJ^A-17)
NIHJ(A-29)
FRI
FRI
S
SUBSTRATE
4 ,16-pregnad iene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3, 20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
4 -andr ostene -3 ,17 -dione
4 -pregnene-3 ,20-d ione
17a -hydroxy-4 -p regnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
11/3,21-dihydroxy-4-pregnene -3,20-dione
REACTION
16
Δ -17-Ac -» 1 7 - C = 0 ; Δ1
11)3-OH
11/3-OH
11/3-OH
2ß-OH
-
6/3-OH;lla-OH
l l a - O H
11/3-OH
17-C = 0 ^ 1 7 a -o x a - 1 7 - C = 0
1 7 ß - A c - 1 7 a -o x a - 1 7 - C = 0
17a-OH-17/3-Ac-*17a-oxa-1 7 - C = 0
17/3-(20-C=O-21-OH)—17a-o x a - 1 7 - C = 0
R E F .
K-450
D-147
D-147
D-147
S-849
S-849
S-849
S-849
S-849
S-846
S-846; S-849
S-846; S-849
S-846; S-849
S-846; S-849
566
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by G e n u s : PYTHIUM RAMULARIA RHACODTUM RHIZOBIUM
(Imperf. - Moniliales) (Imperf. - Mycelia Steri l ia) (Schizo. - Eubacter ia les)
SPECIES
ult imum
RAMULARIA
robusta
RHACODIUM
ce l la re
RHIZOBIUM
leguminosarum
SOURCE
S
Leo P h a r m . P r o d u c t s ,
Denmark
ATCC-13243t
SY
SUBSTRATE
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
l l ß , 1 7 a , 2 1 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione
17/3-hydroxy-4-androsten-3-one
17/3-hydr oxy-17α-methyl -4-androsten -3 -one
17a, 21-d ihydroxy-4-pregnene-3,20-dione
3 -hydr oxy -1 ,3 ,5(10) - e s t r a t r ien -17-one
4 -andros tene -3 ,17-d ione
19-nor -4 -p regnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
1 l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
17a-hydroxy-4-p regnene-3 ,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
l l / 3 , 17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione
4 ,16-pregnad iene-3 ,20-d ione
REACTION
2 0 - C = O -20/3-OH
-
—
1
Δ
Δ
l l a - O H
17-C=0-> 17/3-OH
1 7 - C = 0 -17j3-OH
-
-
-
-
20-C=O-> 2 0 | - O H
2 0 - C = O ^ 20ξ-ΟΗ
2 0 - C = O -20ξ-ΟΗ
R E F .
S-846; S-849
S-846; S-849
S-846; S-849
L-525
L-525
G-313
C-114
C-114
C-114
C-114
C-114
C-114
C-114
C-114
C-114
C-114
TABLE I I I
T ransformat ions by Genus: R H I Z O B I U M
567
SPECIES
meliloti
1 phaseoli
trifolii
SOURCE
SY
SY
SY
SUBSTRATE
3-hydroxy-l,3,5(10)-estratrien-17-one
4-androstene-3,17-dione
19-nor-4-pregnene-3,20-dione
4-pregnene-3,20-dione
1la-hydroxy-4-pregnene-3,20-dione
17a-hydroxy-4-pregnene-3,20-dione
17a,21-dihydroxy-4-pregnene-3,20-dione
ll/3,17a,21-trihydroxy-4-preg-nene-3,20-dione
17a,21-dihydroxy-4-pregnene-3,11,20-trione
4,16-pregnadiene-3,20-dione
3-hydroxy-1,3, 5(10)-estratrien-17-one
4 -androstene -3,17 -dione
19-nor-4-pregnene-3,20-dione
4-pregnene-3,20-dione
1la-hydroxy-4-pregnene-3,20-dione
17a-hydroxy-4-pregnene-3,20-dione
17a,21-dihydroxy-4-pregnene-3,20-dione
l l ß , 17a,21-trihydroxy-4-preg-nene-3,20-dione
17a, 21 -dihydroxy-4-pr egnene-3,11,20-trione
4,16-pregnadiene-3,20-dione
3-hydroxy-l,3,5(10)-estratrien-17-one
4 -androstene -3,17 -dione
REACTION
1 7 - C = 0 -17ß-OH
17-C=0-> 17/3-OH
-
-
-
-
20-C=O-> 20ξ-ΟΗ
20-C=O-> 204-OH
20-C=O^ 20ξ-ΟΗ
-
1 7 - C = 0 -17/3-OH
17-C=0-> 17/3-OH
-
-
-
-
20-C = O-> 20ξ-ΟΗ
20-C=O-> 20ξ-ΟΗ
2 0 - C = O -20ξ-ΟΗ
-
17-C=0 — 17/3 -OH
17-C=0-+ 17/3-OH
REF.
C-114
C-114
C-114
C-114
C-114
C-114
C-114
C-114
C-114
C-114
C-114
C-114
C-114
C-114
C-114
C-114
C-114
C-114
C-114
C-114
C-114
568
T r a n s f o r m a t i o n s by Genus:
TABLE I I I
RHIZOBIUM RHIZOCTONIA
TAXONOMY
(Imperf. - Mycelia Steri l ia)
SPECIES
trifoli i
RHIZOCTONIA (See - Corticium)
ferrugena
SOURCE
SY
ATCC-13246t or
CBS
SUBSTRATE
19-nor -4 -p regnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
11a -hydroxy-4 -p regnene-3 ,20-dione
17a-hydroxy-4-p regnene-3 ,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
11/3,17a, 21- t r ihydroxy-4-pr eg -nene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r ione
4 ,16-pregnad iene-3 ,20-d ione
17/3-hydroxy-4-androsten-3-one
4 -pregnene-3 ,20-d ione
21-hydroxy-4-p regnene-3 ,20-dione
11/3,21 -dihydroxy-4 -pregnene -3,20-dione
17α, 21 -dihydroxy -4 -pregnene -3,20-dione
11a, 17a, 21 - t r ihydroxy-4 -p reg -nene -3 , 20-dione
l l / 3 , 17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
11/3,17a, 21- t r ihydroxy-6a-me thy 1-4 -pregnene-3 ,20-d ione
9 a - f l u o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione
REACTION
—
-
-
-
20-C=O — 20ξ-ΟΗ
2 0 - C = O ^ 20ξ-ΟΗ
20-C=O-> 20ξ-ΟΗ
-
l|3-OH; 2/3-OH
1/3-OH; 2/3-OH
1/3-OH; 2ß-OH
1/3-OH; 2/3-OH
1/3-OH
2ß-OH
1/3-OH; 2/3-OH
1/3-OH; 2/3-OH
1/3-OH; 2/3-OH
1/3-OH; 2/3-OH
1/3-OH; 2/3-OH
R E F .
C-114
C-114
C-114
C-114
C-114
C-114
C-114
C-114
G-313
G-313
G-313
G-313
G-312; G-313; G-315
G-312; G-313; G-315
G-313
G-313
G-313
G-313
G-313
569
TABLE I I I
Transformat ions by Genus: RHIZOCTONIA
SPECIES
ferrugena
munerat i i
solani
SOURCE
ATCC-13246t
ATCC-13247t
ATCC-10154, 10157,10187
ATCC-10157, 10187
SUBSTRATE
17a, 21-dihydroxy-4,9(1 l ) -p regna j d iene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione
17j3-hydroxy-4-androsten-3-one
4 -pregnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17ö, 21-d ihydroxy-4-pregnene-3,20-dione
17/3-hydroxy-4-androsten-3-one
4 -p regnene-3 ,20-d ione
21-hydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
1 1 Ö , 1 7 Ö , 21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
11/3,17a, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
9 a - f l u o r o - l l ß , 1 7 a , 2 1 - t r i h y d r o x y -4-pregnene-3 ,20-d ione
l l / 3 ,17a ,21 - t r i hyd roxy-6 -me thy l -4 -p regnene-3 ,20-d ione
l l / 3 , 1 6 a , 1 7 a , 2 1 - t e t r a h y d r o x y - 4 -p regnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3 ,11 ,20 - t r i one
17a, 21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r i one 21-aceta te
17α, 21 -d ihydroxy-1 ,4 -p regna -d iene-3 ,20-d ione
REACTION
1/3-OH; 2/3-OH
1/3-OH; 2/3-OH
1ξ-ΟΗ; l i a - O H ; 11/3-OH; 11-C = O (via 11/3-OH)
1ξ-ΟΗ; 11α-ΟΗ; 11/3-OH; 1 1 - C = 0 (via 11/3-OH
I4-OH; 11a-OH; 11/3-OH; 11-C= O (via 11/3-OH)
1/3-OH; 11a-OH
Ιξ-OH; l i a - O H ; 11/3-OH; 11-C= O (via 11/3-OH)
1ξ-ΟΗ; 11α-OH; 11/3-OH; 11-C= O (via 11/3-OH)
1ξ-ΟΗ;11α-ΟΗ; 11/3-OH; 11-C= O (via 11/3-OH)
1ξ-ΟΗ; 11α-OH
-
~
-
—
—
—
-
—
R E F .
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
TABLE I I I
T ransformat ions by Genus: RHIZOCTONIA
SPECIES
solani
SOURCE
ATCC-13248t; C3S
ATCC-13249t; CBS
SUBSTRATE
17/3-hydroxy-4-androsten-3-one
4 -pregnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
11a, 17a, 21- t r ihydroxy-4-pr eg-nene-3 ,20-d ione
11/3,17a, 21- t r ihydroxy-4-pr eg -nene-3 ,20-d ione
9 a - f l u o r o - l l ß , 17a,21-tr ihydroxy-4-pregnene-3 ,20-d ione
11/3,17a, 21- t r ihydroxy-6-methy 1-4 -p regnene-3 ,20-d ione
11/3,16a, 17a ,21- te t rahydroxy-4-pr e gnene - 3,2 0 - dione
17a ,21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione
17a, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r i one 21-aceta te
17a, 21-dihydroxy - 1 , 4 - p r e g n a -d iene-3 ,20-d ione
17/3-hydroxy-4-androsten-3-one
4 -pregnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
11a, 17a, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
l l / 3 , 17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
11/3,17a, 21- t r ihydroxy-6-methyI -4 -pregnene-3 ,20-d ione
l l / 3 ,16a ,17a ,21 - t e t r ahydroxy-4-pregnene-3 ,20-d ione
17α, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r ione
REACTION
11a-OH; 11/3-OH
11a-OH; 11/3-OH
l i a - O H ; 11/3-OH; n - c = o (via 11/3-OH)
-
1ξ-ΟΗ
-
-
-
1ξ-ΟΗ
1ξ-ΟΗ
11α-ΟΗ; 11/3-OH; i i - c = o (via 11/3-OH)
1ξ-ΟΗ; 2/3-OH
1ξ-ΟΗ; 2/3-OH
1ξ-ΟΗ; 2/3-OH
-
Ιξ-ΟΗ; 2/3-ΟΗ
1|-ΟΗ; 2/3-ΟΗ
Ιξ-ΟΗ; 2/3-ΟΗ
Ιξ-ΟΗ; 2/3-ΟΗ
Ιξ-ΟΗ; 2/3-ΟΗ
R E F .
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
570
TABLE I I I
T ransformat ions by Genus: RHIZOCTONIA
571
SPECIES
solani
SOURCE
ATCC-13249t; CBS
ATCC-13250t; CBS
C
SUBSTRATE
17a ,21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione 21-aceta te
1 la, 21 -dihydr oxy - 1 , 4 -pr egna -d iene-3 ,20-d ione
17/3-hydroxy-4-androsten-3-one
4 -pregnene-3 ,20-d ione
11/3, 21 -d ihydroxy-4-pregnene -3,20-dione
1 la, 21 -dihydroxy -4 -pregnene -3,20-dione
11a, 1 la, 21 - t r ihydr oxy -4 -pr eg -nene -3 ,20-dione
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
9a- f luoro- l l /3 ,17a , 21- t r ihydr oxy-4-p regnene-3 ,20-d ione
l l j 3 ,17a ,21 - t r ihydroxy-6 -me thy l -4 -p regnene-3 ,20-d ione
l l j 3 , 16a ,17a ,21 - t e t r ahyd roxy -4 -pregnene-3 ,20-d ione
1 la, 21 -dihydr oxy -4 -pregnene -3 ,11 ,20 - t r i one
17o, 21 -d ihydroxy-4-pregnene -3 ,11 ,20 - t r i one 21-ace ta te
1 la, 21 -dihydr oxy - 1 , 4 -pr egna -d iene-3 ,20-d ione
l l / 3 -hydroxy-4 -andros t ene -3 ,17 -dione
REACTION
1ξ-ΟΗ; 2/3-OH
-
1ξ-ΟΗ; 2/3-OH
1ξ-ΟΗ; 2/3-OH
1ξ,15ξ-άίΟΗ
6/3,15^-diOH; 20-C=O -» 20 | -OH
oxidation -products not identified
1ξ-ΟΗ
2/3-OH; 11-C = 0 (via 11/3-OH)
6 /3 -OH; l l -C=0 (via 11/3-OH)
6/3-OH
1ξ-OH; 2/3-OH
1ξ-ΟΗ
-
-
-
1ξ-ΟΗ; 2β-ΟΗ
Ιξ-ΟΗ; 2/3-ΟΗ
2/3,6/3-diOH
-
6/3-ΟΗ
R E F .
G-313
G-313
G-313
G-313
G-312
G-312
G-312
G-313
G-312
G-312
S-793b
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-312
G-313
U-1043
572
TABLE I I I
T ransformat ions by Genus: RHIZOCTONIA
SPECIES
solani (var. lycopersici)
species
SOURCE
CSS
FAKU(B-5; P -20)
IFO (6521)
ATCC-13245
CBS
NRRL-2573
SUBSTRATE
1 7a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-p regnene-3,20-dione
17/3-hydroxy-4-androsten-3-one
4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
l l a , 1 7 a , 2 1 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
l l / 3 , 17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
9a- f luoro- l l /3 , 17a,21- t r ihydroxy-4-pregnene-3 ,20-d ione
l l / 3 ,17a ,21- t r ihydroxy-6 -methyI -4 -p regnene-3 ,20-d ione
l l j 3 ,16a ,17a ,21- t e t r ahydroxy-4-pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione
17a, 21-dihydroxy-4-pregnene -3 ,11 ,20 - t r ione 21-aceta te
17a, 21-d ihydroxy-1 ,4 -p regna-d iene-3 ,20-d ione
17/3-hydroxy-4-androsten-3-one
4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
REACTION
1ξ-ΟΗ
-
1
Δ
6/3-OH
2/3-OH;l la-OH
2/3-OH;l la-OH
lß-OH
2/3-ΟΗ
6/3-OH
2/3-OH;l la-OH
-
2β-ΟΗ
-
-
-
2/3-OH
2/3-OH
-
l l a - O H ; l l / 3 - O H
l l a - O H ; l l / 3 - O H
l l a - O H
11/3-OH
l l / 3 - O H ; l l - C = 0(v ia 11/3-OH)
R E F .
G-313
S-849
T-956
T-956
G-313
G-313
G-313; S-793b
G-312
G-312
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-312; G-313; S-793b
G-312; G-313; S-793b
G-312; G-313 |
TABLE I I I TAXONOMY
573
Transformat ions by Genus: RHIZOCTONIA RHIZOPUS (Phyco. - Mucorales)
SPECIES
species
(from apple)
RHIZOPUS
a r rh i zus
SOURCE
NRRL-2573
FAHU
Rutgers (Dr. Haenseler)
ATCC-11145 UC(RH-176)
SUBSTRATE
11a, 17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
11/3,17a, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
11/3,17a, 21- t r ihydroxy-6-methy l -4 -p regnene-3 ,20-d ione
11/3,16a, 17a ,21- te t rahydroxy-4-pregnene-3 ,20-d ione
17a, 21 -dihydr oxy -4 -pregnene -3 ,11 ,20 - t r ione
17a, 21-dihydr oxy-4-pregnene-3 ,11 ,20 - t r ione 21-ace ta te
17a, 21-dihydr o x y - 1 , 4 - p r e g n a -d iene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17/3-hydroxy-4-androsten-3-one
17/3-hydroxy-17a-methyl-4-andros ten-3-one
4 -andros tene -3 ,17-d ione
4 -andros tene -3 ,17-d ione 6α ,7ξ-Η 3
REACTION
-
1ξ-ΟΗ
-
—
-
1ξ-ΟΗ
1ξ-ΟΗ
11α-ΟΗ; 11/3-ΟΗ; 1 1 - C = 0 (via 11^-OH)
2/3-ΟΗ
74-ΟΗ
15α-ΟΗ
6/3-ΟΗ
Ι ΐα -ΟΗ
6/3-ΟΗ
Ι ΐα -ΟΗ
6/3-ΟΗ
Ι ΐα -ΟΗ
Δ ->5α-Η; 6 - C = 0
6/3-ΟΗ
Ι ΐα -ΟΗ
R E F .
G-313
G-313
G-313
G-313
G-313
G-313
G-313
G-313
S-849
G-312
G-312
E-201
E-201
E-201
E-201
E-201
E-201 ; M-601; M-604; M-636; P-728
M-601; M-604; M-636
B-32
B-32
574
TABLE I I I
T r a n s f o r m a t i o n s by Genus: RHIZOPUS
SPECIES SOURCE SUBSTRATE REACTION REF.
a r rh i zus ATCC-11145 4-pregnene-3 ,20-d ione
17a-hydroxy-4-p regnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione ace ta te
3/3-hydroxy-5a-pregnan-20-one
3ß-hydroxy-5/3-pregnan-20-one
3j3-hydroxy-5-pregnen-20-one
l l o - O H
, Ι Ια -d iOH
6/3-OH
l l a - O H
6/3-OH
l l ö - O H
6/3-OH; 21-OAc -»21-OH
l i a - O H ; 21-OAc| -» 21-OH
7/3-OH
11-OH
7/3,1 la-diOH
7/3,1 la-diOH
F-247; F-248; H-340; L-518; L-519; M-528; M-601; M-611; M-636; N-649; N-682; P -728 ; P -729 ; S-906
H-343; M-601; M-616; N-682; 0 -697 ; 0 -698 ; P-729
M-580
M-601; M-636; M-580
E-203; M-601; M-631; M-636
E-203; P-728
E-203
E-203
E-202; M-601; M-636
M-601; M-636
E-202; M-601; M-628; M-629
E-202; M-601; M-630
TABLE I I I
T ransformat ions by Genus: RHIZOPUS
575
SPECIES
arrhizus
*
*
*
* *
* *
*
SOURCE
ATCC-11145
SUBSTRATE
19 -no r -4 -p regnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
1 7a, 21 -dihydroxy -4 -pregnene -3,20-dione
1 7a, 21 -dihydroxy -4 -pregnene -3 ,20-dione 21-aceta te
1 7 a , 2 1 - d i h y d r o x y - 4 , 9 ( l l ) -p regnadiene-3 ,20-d ione
17a, 21-d ihydroxy-4 ,14-pregna-d iene-3 ,20-d ione
l l /3 ,21-dihydroxy-4 ,17(20)-pregnadien-3 -one
3α, 14/3-dihydroxy-5/3-20(22)-cardenolide
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide (Ref. N-683 - method to acce le ra t e r a t e of hydroxyla-tion)
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide 3-aceta te
3/3,14/3 -dihydroxy -5/3,17a-20(22)-cardenolide
14-hydroxy-3-keto-5/3-20(22)-cardenolide
REACTION
oxidation -products not identified
6/3-OH (0 21 8 )
6j3-OH
l l a - O H
6/3,l la-diOH
l l a - O H ; 21-OAc — 21-OH
no epoxidation
no epoxidation
6/3-OH; 11/3-OH --> n-c=o 3a-OH — 3 - C = 0
1/3-OH
5ß-OH
7ß-OH
X-OH
7ß-OH; 3ß-OH -» 3-C=0
1/3,7/3-diOH
5ß,7ß-diOH
3ß-OAc—3-C=Oj 7ß-OH
3/3-OH — 3 - C = 0
3 -C=0->3a-OH; 7/3-OH
R E F .
3 -71
H-374
M-601; M-615; M-636; N-682; P-725
N-682
N-682
M-645
B-66
B-66
H-341; H-344
N-681
N-682
N-678· N-682
1-425; J-43"2; N-678; N-682; N-683
J-432
N-678
N-682
N-682
N-678
N-681 ; N-682
N-678
576
TABLE I I I
Transformat ions by Genus: RHIZOPUS
SPECIES
a r r h i z u s
cambodjae
chinensis (-)
chiuniang (Yamazaki)
cohnii
SOURCE
ATCC-11145
C
IAM (R-5-6)
NRRL-R-16
SSSR
FAR MIT
SSSR
ATCC-1227b
IAM (10-10)
SSSR
IAM(14-14B)
ATCC-8996
CZAS(I;II)
SUBSTRATE
14/3-hydroxy-3-keto-5/3-20(22)-cardenolide
3j3,7/3,14/3-trihydroxy-5/3-20(22)-cardenolide
3 -keto -bisnor -4 -cholen -22 -a l
(20S)-20-hydroxy-18,20-cycio-4-pregnen-3-one
4 -pregnene-3 ,20-d ione
l l j3 ,21-dihydroxy-4,17(20)-pregnadien-3 -one
Sarsasapogenin
Diosgenin
4-dehydrotigogenone
17a, 21-d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
17o-hydroxy-4-pregnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
17«, 21-dihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
11/3,21 -dihydroxy -4,17(20)-pr egnadien -3 -one
4 -pregnene-3 ,20-d ione
REACTION
7/3-OH
3/3-OH->3-C=0
6/3,1 la -d iOH; 2 2 - C = 0 -22-OH
11a-OH
l l a - O H
6/3-OH;ll/3-OH - + i i - c = o
---
6/3-OH
l l a - O H
6 ß , l l a - d i O H
6/3,1 la-diOH
oxidation
oxidation
oxidation
oxidation
l l a - O H
6/3-OH
l l a - O H
6j3-OH;ll/3-OH
-n-c=o l l a - O H
R E F .
N-678
N-678
M-578
W-1071
A-29
H-341
M-587
M-587
M-587
E-224
C-84
C-84
E-224
M-601; M-636
M-601; M-636
M-601; M-636
M-601; M-636
A-26; A-29
E-224
A-29
H-431
T-1028
TABLE I I I
577
T r a n s f o r m a t i o n s by G e n u s : RHIZOPUS
SPECIES
cohnii
de lemar
1 *
1 * 1 * 1 *
1 *
delemar
formosens is (formosaensis)
japonicus
SOURCE
SSSR
U
ATCC-4858
IAM (19-27)
NI
U
IAM(24-29C) (Nakazawa)
ATCC-8446
SUBSTRATE
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
4 -p regnene-3 ,20-d ione
17a -hydroxy-4 -p regnene -3 ,20 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
11/3,21-dihydroxy-4,17(20)-pregnadien-3-one
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide
14/3-hydroxy-3-keto-5/3-20(22)-cardenolide
4 -p regnene-3 ,20-d ione
17a -hydroxy-4 -p regnene -3 ,20 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4 -p regnene-3 ,20-d ione
l l /3 ,21-dihydroxy-4 ,17(20)-pregnadien-3 -one
REACTION
6/3-OH; l l a - O H ; 11/3-OH
oxidation
oxidation
oxidation
oxidation
6/3-OH; 11/3-OH ^n-c=o 11a-OH
l l a - O H
6/3,1 la -d iOH
6ß-OH
l l a - O H
1/3-OH
3/3-OH—3-C = 0
7/3-OH
5ß,7/3-diOH
7ß-OH
oxidation
oxidation
oxidation
oxidation
l l a - O H
6/3-OH; 11/3-OH -n-c=o
R E F .
E-224
M-601; M-636
M-601; M-636
M-601; M-636
M-601; M-636
H-341
A-29
N-682
N-682
N-682
N-682
N-682
N-682
N-682
N-682
N-682
M-601; M-636
M-601; M-636
M-601; M-636
M-601; M-636
A-29
H-341
578
TABLE I I I
T r a n s f o r m a t i o n s by Genus: RHIZOPUS
SPECIES
japonicus
javanicus
*
*
* *
*
*
kansho (Yamamoto)
kasanens is
n igr icans
SOURCE
IAM(24-14; 24-14B)
U
IAM(26-23)
NI
IAM(28-14)
ATCC-8998
U
ATCC-6227a
SUBSTRATE
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
17a-hydroxy-4-p regnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
3/3,14/3-dihydroxy-5ß-20(22)-cardenolide
14/3-hydroxy-3-keto-5/3-20(22)-cardenolide
4 -pregnene-3 ,20-d ione
11/3,21-dihydroxy-4,17(20)-pregnadien-3 -one
4-pregnene-3 ,20-d ione
17a-hydroxy-4-pregnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
3/3-hydroxy-5-pregnen-20-one
REACTION
l i a - O H
oxidation
oxidation
oxidation
oxidation
l i a - O H
6/3,1 la -d iOH
l i a - O H
6/3 -OH
11α-ΟΗ
7/3-OH
1/3-OH
3/3-OH-»3-C=0
7/3-OH
11a-OH
6/3,1 la-diOH
6/3-OH-l 1/3-OH -ai-c=o
oxidation
oxidation
oxidation
oxidation
oxidation -products not identified
R E F .
A-29
M-601; M-636
M-601; M-636
M-601; M-636
M-601; M-636
A-29
N-682
N-682
N-682
N-682
N-682
N-682
N-682
N-682
A-29
A-26
H-341
M-601; M-636
M-601; M-636
M-601; M-636
M-601; M-636
T-1028
TABLE ! I l
579
T r a n s f o r m a t i o n s by G e n u s : RHIZOPUS
SPECIES
nigr icans
(see stolonifer)
(in mixed cul ture with Pénic i l l ium lilacinum [17/3-Ac—» 17/3-OH])
SOURCE
ATCC-6227a
ATCC-6227b
SUBSTRATE
4-pregnene-3 ,20-d ione
17a-hydroxy-4-p regnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17/3-hydroxy -4 - e s t r en -3 -one
17/3-hydr oxy- 17a -methyl - 4 -e s t r en -3 -one
17/3-hydroxy -4 -androsten -3 -one
17/3-hydroxy-17a-methyl-4-andros ten-3-one
REACTION
l l a - O H
l l a - O H
l l a - O H
oxidation -products not identified
l l a - O H
oxidation -products not identified
6/3-OH
10/3-OH
l l a - O H
l l ö - O H
6/3-OH
l i a - O H
6β-ΟΗ
l i a - O H
11α-OH
R E F .
M-601; M-636; T-1028
M-636
M-636
T-1028
M-636
T-1028
M-642; P-708
M-642; P-708
M-619; M-620; P-708
M-575; M-608
E-201
E-201 ; M-601; M-619; M-620; M-636
E-198; E-201 ; M-619
E-201 ; M-575; M-608; M-624; M-626; M-638
S-831
580
TABLE I I I
Transformat ions by Genus: RHIZOPUS
SPECIES SOURCE SUBSTRATE REACTION R E F .
n igr icans
(in mixed cul ture with Pénici l l ium li lacinum [17/3-Ac-
17-C=OJ)
ATCC-6227b 4 -andros tene-3 ,17-d ione
3/3-hydroxy-5a-pregnan-20-one
6/3-hydroxy-3a, 5a-cyclopregnan-20-one
5a-pregnane-3 ,20-d ione
5/3-pregnane-3,20-dione
5/3 -pregnane -3 ,20-dione 11α,12α-Η3
5 /3 -pregnane-3 ,20-d ione- l l a -D
5/3-pregnane -3 ,20-dione -11/3-D
16a, 1 la- oxido- 5a -pregnane -3,20-dione
16a, 17a -oxido -5/3 -pregnane -3,20-dione
3/3-hydroxy-5-pregnen-20-one
20a-hydroxy-4-pregnen-3-one
20/3-hydroxy-4-pregnen-3-one
(20S)-20-hydroxy-18,20-çy_çlp-4-pregnen-3-one
19-nor -4 -p regnene-3 ,20-d ione
6/3-OH
l i a - O H
l i a - O H
l i a - O H
7/3,1 la-diOH
l l a - O H
l l a - O H
l l a - O H
l i a - H -l l a - O H
l l a - O H ( loss of l l a - D )
l l a - O H (11/3-D)
l l a - O H
l l a - O H
7/3-OH l l a - O H
l l a - O H
no oxidation at C - l l
l l a - O H
E-201
E-201 ; M-601; M-636
S-831
M-601; M-636
M-601; M-636
W-1069; W-1070
E-209; M-601; M-636
E-209; M-601; M-636
H-371
C-137
C-137
K-439
K-440; W
E
S-
S-
-1066
-202
832
832
W-1071
B - 7 1 ; B-73; C-117; C-118; M-636
TABLE I I I
581
T r a n s f o r m a t i o n s by G e n u s : RHIZOPUS
SPECIES SOURCE SUBSTRATE REACTION R E F .
n i g n c a n s ATCC-6227b
(in mixed cul ture with Pénici l l ium li lacinum [17/3-Ac-» 17-C=Ol)
4 -pregnene-3 ,20-d ione 11a-OH
l l a - O H ; Δ -» 5a-H
6/3, l la-diOH
l l û - O H
17a-hydroxy-4-p regnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione aceta te
16a-methy l -4 -p re gnene -3 ,20 -dione
16ß-me thy l -4 -p regnene -3 ,20 -dione
6/3-f luoro-17a-hydroxy-4-preg-nene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
E-200; M-601; M-611; M-636; N-650; N-682; P -729 ; R-766; T-1028; W-1069; W-1106
P-729
N-682; P -729 ; W-1069
S-831
6/3-OH
l l a - O H
11a-OH
l l a - O H
l l a - O H ; ^ 2 1 - O H
l l a - O H
(o218)
21-OAc
M-580; M-601; M-607; M-613
E-200; H-391; M-580; M-601; M-607; M-627; M-636
E-203; M-601; M-636
H-374
E-203; M-601; M-636
C-141; L-515; L-517; S-804
l l a - O H
l l a - O H
6/3-OH
L-517
H-
M N-P -
-391
-615; -682; 725
582
TABLE I I I
T r a n s f o r m a t i o n s by Genus: RHIZOPUS
SPECIES
nigr icans *
SOURCE
ATCC-6227b
SUBSTRATE
17a,21 -dihydroxy -4 -pregnene -3,20-dione
1 7a, 21 -dihydroxy -4 -pregnene -3,20-dione 21-aceta te
17a-hydroxy-21-methy l -4 -preg-nene-3 ,20-d ione
21-hydroxy-17a-methy l -4 -preg-nene-3 ,20-d ione aceta te
6α, 16a-d imethyI-4-pregnene-3,20-dione
16a, 17a-méthylène-4-pregnene-3,20-dione
16a, 17a-ox ido-4-pregnene-3 ,20-dione
6a-ch loro-16a , 17a-méthylène -4 -pregnene-3 ,20-d ione
6/3-fluoro-17a-hydroxy-21-methyl -4 -pregnene-3 ,20-d ione
6a-f luoro-16a, 17a-méthylène -4-pregnene-3 ,20-d ione
6/3 -f luor o -16a, 17a -méthylène -4-pregnene-3 ,20-d ione
21-hydroxy-16a ,17a-oxido-4-pregnene-3 ,20-d ione aceta te
17α, 21 -dihydroxy - 7 - methyl -4 -p regnene-3 ,20-d ione 2 1 -aceta te
6a - methyl -16a, 17a - méthylène -4-pregnene-3 ,20-d ione
REACTION
l i a - O H
l i a - O H ; Δ-+ 5/3-H
l l a - O H ; 2 1 - O A c - 2 1 - O H
l i a - O H
l l a - O H
l i a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H ; 21-OAc ^ 2 1 - O H
l l a - O H ; 21-OAc —21-OH
l l a - O H
R E F .
E-200; M-601; M-636; M-641; M-645; N-682; P-725
M-601; M-606; M-636; P-725
M-601; M-636; M-641; M-645
H-391
H-377
S-923
C-92
B-52; D-160; D-161; E-223; M-644; P-727
C-92
H-391
C-92
C-92
A-8
B-33
C-92
TABLE I I I
Transformat ions by Genus: RHIZOPUS
583
SPECIES
nigr icans
SOURCE
ATCC-6227b
SUBSTRATE
6a-f luoro-17a ,21-d ihydroxy-16-me thy lene -4 -p regnene -3 ,20 -dione 21-aceta te
17α, 21-dihydroxy-βα, 16α-di-methy l -4 -pregnene-3 ,20-d ione
21-hydroxy-16a ,17a-oxido-4-pregnene-3 ,20-d ione
21-hydroxy-17a-methy l -1 ,4 -pregnadiene-3 ,20-d ione aceta te
16α, 17α -méthylène - 1 , 4 -pregna -d iene-3 ,20-dione
6a-ch loro-16a , 17a-méthylène -1,4 -pregnadiene -3 ,20 -dione
6a-f luoro-16a, 17a-méthylène-1,4 -pr egnadiene -3 ,20-dione
6ß - f lu or o -16a, 17a - méthylène -1,4-pr egnadiene-3 ,20-dione
6a-methyl -16a , 17a-méthylène-1,4 -pr egnadiene-3,20-dione
17a, 21 -dihydroxy- 6a, 16a -d i -methyl -1 ,4 -pr egnadiene - 3 , 20-dione 21-aceta te
6a- f luoro-16a ,17a ,21- t r ihydroxy-1,4 -pr egnadiene -3 ,20-d ione
4 , 6 - p r egnadiene-3 ,20-dione
6-chloro-16a, 17a-méthylène-4 , 6-pr egnadiene-3 ,20-dione
16a, 17a-méthylène-4 , 6-pregna-d iene-3 ,20-d ione
6-methyl-16a, 17a-méthylène -4 , 6 - p r egnad iene-3 ,20-dione
17a, 21-d ihydroxy-4 ,14-pregna-d iene-3 ,20-d ione
4 , 16 - p r egnadiene-3 ,20-dione
REACTION
l i a - O H · 2 1 -OAc-21 -OH
l i a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H ; 2 1 -O A c - 2 1 -OH
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
no epoxidation
16
11α-ΟΗ; Δ -17-Ac-+17a-Ac
R E F .
A-7
S-903
F-243
H-377
C-92
C-92
C-92
C-92
C-92
S-903
R-771
D-178; M-601; M-621; M-636; P-730
C-92
C-92
C-92
B-66
M-579; M-601; M-605; M-612; M-636
584
TABLE I I I
T r a n s f o r m a t i o n s by Genus: RHIZOPUS
SPECIES SOURCE SUBSTRATE REACTION R E F .
n igr icans ATCC-6227b
ATCC-7577
ATCC-10404
1 ,4 ,6 -p regna t r i ene -3 ,20-d ione
1 6 a , 1 7 a - m e t h y l e n e - l , 4 , 6 -p regna t r i ene -3 ,20-d ione
6 - chlor o -16a ,17a- méthylène -1 , 4 , 6 - p r e g n a t r i e n e - 3 , 2 0 -dione
6-f luoro-16a, 1 la -méthylène -1 , 4 , 6 - p r e g n a t r i e n e - 3 , 2 0 -dione
6 -methyl -16α, 1 la - méthylène -1 , 4 , 6 - p r e g n a t r i e n e - 3 , 2 0 -dione
14/3-hydroxy-3-keto-5/3-20(22)-cardenolide
3j3,14/3-dihydroxy-5/3-20(22)-cardenolide (Ref. N-683 - method to acce le ra te hydr oxy lation)
b i snor -4 -cho len-22-a l -3 -one
4-pregnene-3 ,20-d ione
1 la -hydroxy-4-pr egnene-3 ,20-dione
21-hydroxy-4-pregnene-3 ,20-dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
4-pregnene-3 ,20-d ione
17a-hydroxy-4-pregnene-3 ,20-dione
l i a - O H
l l a - O H
l i a - O H
l l a - O H
l l a - O H
7/3-OH
1/3-OH
H-388; O-700
C-92
C-92
C-92
C-92
N-682
N-682;
7/3-OH
1/3,7/3-diOH
5/3,7/3-diOH
3/3-OH->3-C=0
l l a - O H ; 22-C= 0 ^ 2 2 - O H
6/3,1 l a -diOH; 2 2 - C = 0 — 2 2 -OH
15a-OH; 22-C= O - » 22-OH
l l a - O H
l l a - O H
N-683
N-682; N-683
N-682
N-682
N-682
M-578; M-601; M-622; M-636
M-578; M-601; M-636
E-202
M-601
M-636
l l a - O H
l l a - O H
l l a - O H
l l a - O H
M-636
M-636
M-601
M-636
TABLE I I I
585
T r a n s f o r m a t i o n s by G e n u s : RHIZOPUS
SPECIES
nigr icans
(in mixed cul ture with
chus [21 -OH ] and Tr icothecium ro seum [17a-OH|)
(in mixed cul ture with low yielding s t r a in of
1 Bacil lus subtl is -Δ1)
SOURCE
ATCC-10404
Char les
CZAS
FRI
Hoechst
SUBSTRATE
21-hydroxy-4 -p regnene -3 ,20 -dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
19 -nor-4 -pr egnene -3 ,20-dione
l l /3 ,21-dihydroxy-4 ,17(20)-pregnadien-3 -one
3/3,21 -dihydr oxy - 5a -pr egnan-20-one
d , l - 4 -p regnene -3 ,20 -d ione
4 -pregnene-3 ,20-d ione
18-hydroxy-4-p regnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
1 Ία, 21 -dihydr oxy -4 -pregnene -3,20-dione
4 -pregnene-3 ,20-d ione
3 ß - hydr oxy - 3 - nor- 5 - andr osten -17-one
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
REACTION
11a-OH
l l a - O H
oxidation -products not identified
6/3-OH; 11/3-OH -» n-c=o 7/3-OH
d , l ^ d - l l a - O H + 1
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
Δ 5 - 5 ξ , 6ξ-oxide
l l a - O H
l l a - O H ; Δ 5 -5 ξ , 6 | -ox ide
Δ^->5ξ, 6 4 -oxide—»5a, 6/3-diol
15a-OH
X-OH
6/3-OH; l l a - O H
Δΐ ( inc reased yield)
R E F .
M-636
M-636
3 - 7 1
H-341
K-433
W-1102
W-1106
W-1100
K-433
K-433
T-1028
P-741
P-741
P-741
P-741
P-741
P-741
S-849
L-521
Ophioboius herpotri-
586
TABLE I I I
Transformat ions by Genus:· RHIZOPUS
SPECIES
nigr icans (in mixed cul ture with low yielding s t r a in of Bacillus subti l is [Δ1] )
( Yamazaki)
(Ehrenberg)
SOURCE
Hoechst
IAM (R-5-4; R - 5 - 7 ; 37-12; 37-27)
IPB
NG (Brit . Drug Houses - No.
153)
NG
NG (Sandoz)
NRRL-1478
NRRL
PIRI
SSSR (VNIKH-F-1-7)
( F - l )
SUBSTRATE
l l j3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3 ,11 ,20- t r ione
4-pregnene-3 ,20-d ione
(use of Warburg s tudies a s in-dicator of t ransformat ion -Ref. C-106)
20/3-hydroxy-3-keto-4-pregnen-18-oic acid (18-+20) lactone
17/3-hydroxy-4-methyi-4-andros ten-3-one
16α,17α -ox ido-4 -p regnene-3 ,20-dione
3/3,6/3,8/3,14/3-tetrahydroxy-4, 20,22-bufatr ienolide 6 -acetate 3-glucoside
1 6 a , 1 7 a , 2 1 - [ 3 , l , l - ( 2 - p y r a z o -lino) 1-4-pr egnene-3 ,20-dione
Sarsasapogenin
Diosgenin
4-dehydrotigogenone
4 -p regnene-3 ,20 -dione
4 -pregnene-3 ,20-d ione
REACTION
Δ1
Δ1
11a-OH
11a-OH
7 ξ - Ο Η
l l a - O H
6/3-OH
7a-OH
7/3-OH
l l a - O H
l l a - O H
3/3-[l1 4-glucoside -» 3/3-OH]
l l a - O H
l l a - O H ; 6/3,11a -diOH
l l a - O H
l l a - O H
R E F .
L-521
L-521
A-29
C-103; C-106; C-107
L-488; L-489
L-488; L-489
K-445
K-445
K-445
K-445
E-223
S-936a
W-1113
M-587
M-587
M-587
W-1115
B-42
T-1011
TABLE I I I
Transformat ions by Genus: RHIZOPUS
587
SPECIES
nigr icans
niveus (Yamazaki)
1 nodosus 1 (Namyslowski )
1 oryzae
1 pseudochinensis
1 ( Yamalaki )
pygmaeus
1 ref lexus
SOURCE
Moscow (very active s t r a in s - 1 , 7 , 1 0 , 1 6 , 1 7 , 1 8 ,
19,58)
(poorly active - 2 , 5 , 6 , 8 , 1 1 , 12,13,14)
SSSR
WC(86)
TSURUMI
IAM (R-5-5 )
IAM (32-29)
ATCC-9363 and
10260
IAM (R-5-7)
CZAS
IAM
SSSR
ATCC-1225
SUBSTRATE
4-pregnene-3 ,20-d ione
6/3-f luoro-17a,21-dihydroxy-4-pregnene-3 ,20-d ione
4 , l l - p r e g n a d i e n e - 3 , 2 0 - d i o n e
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
17ö-hydroxy-4-pregnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
17«, 21-d ihydroxy-4-pregnene-3,20-dione
17j3-hydroxy-4 - e s t r en -3 -one
REACTION
l i a - O H ; 6/3, l l o - d i O H
l l a - O H
6/3,1 lu-diOH; 11/3-OH; l l a - O F
l l ö - O H
no epoxidation
l l a - O H
l l o - O H
11-oxygénation
11-oxygénation
11-oxygénation
11-oxygénation
l l a - O H
l l a - O H
l l a - O H
6/3-OH
6/3-OH; Δ 4 -* Δ5; ketoniz.
6/3-OH
l l a - O H
R E F .
T-1010
E-224; S-946; T-1009
T-1009; E-224
F-268
K-484
A-29
A-29
M-601; M-636 M-601; M-636
M-601 ; M-636
M-601; M-636
A-29
T-1028
A-29
E-224
M-623
M-618; M-620
M-618; M-620
588
TABLE I I I
Transformat ions by Genus: RHIZOPUS
SPECIES
reflexus
shanghaiesis (shanghaiensis)
species
SOURCE
ATCC-1225
U
ATCC-10329
U
C
SUBSTRATE
17/3-hydroxy-4-androsten-3-one
17/3-hydroxy-17a-me thy 1-4-andros ten-3-one
4 -andros t ene -3 ,17-d iene
16α, 17a-ox ido-4-pregnene-3 , 20-dione
4-pregnene-3 ,20-d ione
17a-hydroxy-4-p regnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
l l /3 ,21-dihydroxy-4 ,17(20)-pregnadien-3-one
3/3-hydroxy-14a,15a-oxido-20(22)-cardenolide aceta te
4 -p regnene-3 ,20-d ione
17a-hydroxy-4-p regnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
3/3,21 -d ihydroxy-5a-pregnan-20-one
4 -pregnene-3 ,20-d ione
21-hydroxy-4 -p regnene-3 ,20-dione
REACTION
6/3-OH
3-C = 0 - A 4 -5 a - H - 3 , 6 - d i -C = 0 (via 6/3-OH; Δ4-*Δ5; ketoniz. )
l l a - O H
6/3-OH
l l a - O H
6/3-OH
l l a - O H
l l a - O H
11-OH
11-OH
11-OH
11-OH
6/3-OH; 11/3-OH
- n-c=o 3/3-OAc^3j3-OH
11-oxygénation
11-oxyge nation
11-oxygenation
11-oxygénation
7/3-OH
l l a - O H
l l a - O H
R E F .
E-201 ; M-618
E-201 ; M-623
E-201
E-201
E-201
E-201
E-201
M-644
M-601; M-636
M-601; M-636
M-601; M-636
M-601; M-636
H-341
M-576; M-577
M-601; M-636
M-601; M-636
M-601; M-636
M-601; M-636
K-433
K-433
K-433
TABLE I I I
589
T r a n s f o r m a t i o n s by Genus: RHIZOPUS
SPECIES
species
1 stolonifer (synonym for n i g r i -cans)
1 stolonifer in abs t r ac t (n ig r i cans - inRef . T-1011)
SOURCE
C
IAM
NRRL
Sear le
SSSR
SY
ATCC-6227b
SSSR (No. 7,16)
SUBSTRATE
d , l - 2 1 - h y d r o x y - 4 - p r e g n e n e - 3 , 20-dione
17a ,21-hydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
plant saponins
3/3- hydroxy - 5 -andr osten -17 -one
4 -andros tene -3 ,17-d ione
4 -p regnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -andros tene -3 ,17-d ione
17a-methyl th io-4-andros ten-3-one
17/3 -methy Isulf iny 1 -4 -andr osten -3-one
17)3-methylsulfonyl-4-androsten-3-one
4 -p regnene-3 ,20-d ione
REACTION
d,l-> d-6/3-OH + 1
l i a - O H
l i a - O H
7a-OH
7/3-OH
7 - C = 0
6/3-OH; l l a - O H
l i a - O H
6/3, l la-diOH
l l a - O H
7/3-OH
l l a - O H ; 17a-SCH3—17a-S(0)CH3
17a-SCH3 -> 17a-S(0)CH3 ( s te reochemis t ry a t S unknown)
1 7 a - S C H 3 ^ 17a-S(0)CH3 (opposite s t e r eo -chemis t ry at S from preceding compound)
Πα-ΟΗ (s te reochemis t ry at S unknown)
l l a - O H (opposite s te reo-chemis t ry a t S from preceding compound)
l l a - O H
l l a - O H
R E F .
W-1102
K-433
A-29
K-478
D-175
D-175
D-175
D-175
T-1010
T-1010
M-554
T-1037
D-174; D-176
D-174
D-174
D-176
D-176
D-176
T-1011
590
TABLE I I I
T r a n s f o r m a t i o n s by Genus: RHIZOPUS RHODOSEPTORIA
TAXONOMY
(Imperf. - Sphaeropsidales)
SPECIES
suinus
tonkinensis
t r i t i c i
RHODOSEPTORIA
1 spec ies
SOURCE
C
IAM (65-10)
SSSR
U
ATCC-1230
IAM (65-5a ; 66-14c; 66-27)
U
ATCC-11833 QM-704
SUBSTRATE
21-hydroxy-4-p . regnene-3 ,20-dione
4-pregnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
4-pregnene-3 ,20-d ione
1 l a -hydroxy-4 -p regnene -3 ,20 -dione
21-hydroxy-4 -p regnene-3 ,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
11/3,21 -dihydroxy-4,17(20) -pr e gnadien - 3 - one
4 -pregnene-3 ,20-d ione
17a-hydroxy-4-p regnene-3 ,20-dione
21-hydroxy-4-p regnene-3 ,20-dione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
17a-hydroxy-4-pregnene-3 ,20-dione
21-hydroxy-4-p regnene-3 ,20-dione
17a, 21-dihydroxy-4-pregnene -3 ,20-dione (use of whole broth or washed mycelium)
REACTION
17]3-(20-C-O-21-OH)-* 1 7 - C = 0
l l a - O H
6/3-OH
11-oxygénation
11-oxygénation
11-oxygénation
11-oxygénation
6/3-OH; 11 /3-OH-n-c=o l l a - O H
oxidation
oxidation
o xidation
oxidation
11/3-OH
11/3-OH
11/3-OH
R E F .
W-1095
A-29
E-224
M-601; M-676
M-601; M-636
M-601; M-636
M-601; M-636
H-341
A-29
M-601; M-636
M-601; M-636
M-601; M-636
M-601; M-636
K-446
K-446
K-446
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by G e n u s : RHODOTORULA (imperf. - Monmaies)
591
SPECIES
RHODOTORULA
glutinis
grac i l i s
longiss ima
SOURCE
IFO (0395)
NRRL
SQ (SC-2218)
NRRL-Y-2343
SUBSTRATE
11/3,17a-dihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
1 7 a , 1 9 , 2 1 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
1 7 a , 2 1 - d i h y d r o x y - l , 4 - p r e g n a -d iene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
4 -pregnene-3 ,20-d ione
5-cholesten-3/3-01
4 -p regnene-3 ,20-d ione
1 l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
l l / 3 -hydroxy-4 -p regnene-3 ,20-dione
17a -hydroxy-4 -p regnene-3 ,20-dione
17/3-hydr oxy -17a -4 -p regnene -3,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
11/3,17a-dihydroxy-4-pregnene-3,20-dione
1 I ß , 21-dihydr oxy-4-p regnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
11a, 17a, 21 - t r ihydroxy-4 - p r e g -nene -3 ,20-d ione
11/3,17a, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
REACTION
20-C = O ^ 20a-OH
2 0 - C = O -20a-OH
20-C=O-> 20a-OH
2 0 - C = O -20a-OH
-
-
-
-
Δ ^ Δ ;3/3-OH - 3 - C = 0
2 0 - C = O -20a-OH
20-C=O-> 20a-OH
20-C=O-> 20a-OH
2 0 - C = O -20a-OH
-
-
20-C = O ^ 20a-OH
-
20-C=O — 20a-OH
2 0 - C = O ^ 20a-OH
20-C=O-> 20a-OH
2 0 - C = O - * 20a-OH
R E F .
T-958
T-958
T-958
T-958
M-587
M-587
M-587
T-1005
T-1005
C-122
C-122
C-122
C-122
C-122
C-122
C-122
C-122
C-110; C-122
C-122
C-122
C-122
592
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: RHODOTORULA ROSSELLINIA
RUSSULA SACCHAROMYCES
(Asco. - Sphaeriales) (Basidio. - Agaricales) (Asco. - Endomycetales)
SPECIES
longissima
(rubra)
ROSSELLINIA
necat r ix
RUSSULA
delicans
SACCHAROMYCES
NOTE: L i t e ra tu re i s not always c lear on name of spec ies ; top or bot-tom yeas t , b a k e r s , b r ewer s or impover -ished yeas t , nor i s it cer ta in that al l were s t r a ins of ce rev i s i ae . Wherever poss ible the original source and type a r e given.
ce rev i s iae
SOURCE
NRRL-Y-2343
TNAES
ALiC-173)
ATCC-4125
SUBSTRATE
17ö-hydroxy-4 -p regnene-3 ,11 , 20- t r ione
17a ,21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione
17o ,21 -d ihyd roxy - l , 4 -p r egna -diene - 3 , 1 1 , 2 0 - t r i o n e
17a-hydroxy-9j3,11/3-oxido-1 ,4 ,6 -pregnat r iene - 3 , 2 0 -dione
17a,21-dihydroxy-9/3,11/3-oxido-l , 4 , 6 - p r e g n a t r i e n e - 3 , 2 0 -dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
Note on React ions Attr ibuted to Yeas t : In the y e a r s 1937-1938 many oxidations of s t e ro ids were er roneously repor ted to be c a r -r i ed out by yeas t (see Ref. V-1047). Later work showed that these reac t ions were due to spec ies of corynebac te r ia and f lavobacteria which were con-taminants in the yeas t p r e p a r a -t ions (see Ref. A-17).
Transformat ions r epor t ed in this table show only t h o s e reac t ions actually c a r r i e d out by yeas t . All o thers may be found under the appropr ia te bac te r ia l genus.
l , 4 - and ros t ad i ene -3 ,17 -d ione
9c*-fluoro -1 lß-hydroxy - 1 , 4 -andros tad iene-3 ,17-d ione
REACTION
20-C=O-> 20a-OH
2 0 - C = O -20a-OH
2 0 - C = O ^ 20a-OH
2 0 - C = O -20a-OH
2 0 - C = O -20a-OH
oxidation -product not identified
1 7 - C = 0 -17/3-OH
1 7 - C = 0 -17/3-OH
R E F .
C-122
C-122; C-110
C-110
G-303
G-303
S-849
S-825
A-17; K-457; M-552; M-594; V-1047
A-17; E-219; E-220; M-538; M-546; M-553
C-128
N-666
TABLE I I I
T ransformat ions by Genus: SACCHAROMYCES
593
SPECIES
ce rev i s i ae
(dist i l lers)
SOURCE
ATCC-4125
FAR MIT
SUBSTRATE
9a - f luor o -11 ß - hydr oxy -16a -me thy l -1 ,4 -andros tadiene -3,17-dione
9 a - b r o m o - 1 6 a - m e t h y l - 1 , 4 -and ros t ad i ene -3 ,11 ,17 - t r i one
9a-chlor o -16a -me thy l -1 ,4 -and ros t ad i ene -3 ,11 ,17 - t r i one
9 a - f l u o r o - 1 6 a - m e t h y l - l , 4 -and ros t ad i ene -3 ,11 ,17 - t r i one
l l / 3 - h y d r o x y - l , 4 , 6 - a n d r o s t a -t r i ene -3 ,17 -d ione
9a- f luoro-11/3-hydroxy-1 ,4 ,6-andros t a t r i ene -3 ,17 -d ione
l , 4 , 6 - a n d r o s t a t r i e n e - 3 , 1 1 , 1 7 -t r ione
9a -f luoro - 1 , 4 , 6 - andros ta t r iene -3 ,11 ,17 - t r i one
1 ,4 ,9 (11 ) - and ros t a t r i ene -3 ,17 -dione
3ß-hydroxy-16a ,17a-ox ido-5a-pregnan-20-one
l l a - h y d r o x y - 5 a - p r e g n a n e - 3 , 2 0 -dione
l l a - h y d r o x y - 5 a - p r e g n a n e - 3 , 2 0 -dione ace ta te
1 l a -hyd r oxy - 5/3-pr e g n a n e - 3 , 2 0 -dione
17a-hydr oxy-5/3-pr egnane -3 ,20 -dione
21-hydroxy-5/3-pregnane-3 ,20-dione
16a ,17a-oxido-5 /3-pregnane-3 ,20-dione
11/3,17a, 21- t r ihydr oxy-5a-pr eg-nane-3 ,20-d ione 21-ace ta te
REACTION
1 7 - C = 0 -17/3-OH
1 7 - C = 0 - > 17/3-OH
1 7 - C = 0 ^ 17/3-OH
1 7 - C = 0 - > 17/3-OH
1 7 - C = 0 - * 17/3-OH
1 7 - C = 0 -17/3-OH
1 7 - C = 0 -17/3-OH
1 7 - C = 0 - > 17/3-OH
1 7 - C = 0 -17/3 -OH
16α,17α-oxide - 1 6 a - O H ; 1 3 / 3 -CH3->17/3-CH3; 2 0 - C = O - 2 0 a -OH; Δ1 3
3-C = 0 ^ 3 / 3 - O H
no reduction
no reduction
no reduct ion
no reduct ion
16a,17a-oxide-+ 16a-OH;13/3-CH3 — 17/3-CH3; 20-C = O - 2 0 a - O H :
>13
no reduction
R E F .
R-752
R-752
R-752
R-752
G-305
G-305
G-305
G-305
R-775
C-88
C-83; C-89
C-83
C-83
C-83
C-83
C-88; C-90
C-83
594
TABLE I I I
Transformat ions by Genus: SACCHAROMYCES
SPECIES
cerev i s iae (dis t i l lers)
(bread yeast)
(bakers yeast)
SOURCE
FAR MIT
FAR MIT
Kaiser Wihelm I n s t . , Ber l in
SUBSTRATE
5a -pr egnane - 3 , 1 1 , 2 0 - t r ione
5/3-pregnane-3,11,20- t r ione
17a, 21 -dihydroxy - 5a -pr egnane -3 ,11 ,20 - t r ione 21-ace ta te
3/3-hydroxy-16a, 17a-oxido-5-pregnen-20-one
20/3-hydroxy-16a, 17a-oxido-4-pregnen-3-one
l l a - h y d r o x y - 1 6 a , 1 7 a - o x i d o - 4 -pregnene-3 ,20-d ione
16a, 17a-ox ido-4-pregnene-3 ,20-dione
4 -p regnene -3 ,11 ,20 - t r i one
3j3,20j3-dihydroxy-4j3, 5j3-oxido-pregnane
3/3-hydroxy-5a, 6a-oxido-pregnan-20-one
3/3,21-dihydroxy-16a, 17a-oxido-5-pregnen-20-one 21-aceta te
4/3, 5j3-oxidopr egnane-3 , 20-dione
l ,3 ,5 (10) -es t r a t r i ene -3 ,17 /3 -d io l propionate
3 - h y d r o x y - l , 3 , 5 ( 1 0 ) - e s t r a t r i e n -17-one aceta te
3 - h y d r o x y - l , 3 , 5 ( 1 0 ) - e s t r a t r i e n -17-one propionate
REACTION
3 - C = 0 -3a-OH
3 - C = 0 - * 3a-OH
no reduction
16a, 17a -oxide -♦ 16a-OH;13/3-CH3 ^17/3-CH3; 20-C = 0 — 20a-OH; Δ13
-
-
16a,17a-oxide-^ 16a-OH; 13ß-CH3 ^17j3-CH,; 20-C=O^>20a3-OH; Δ1 3
no reduction
4/3, 5/3-oxido— 4j3,5a-diol
5a,6a-oxido—» 5a,6j3-diol
16a, 17a- oxide —» 16a-OH; 13ß-CH3 ^ 1 7 ß - C H 3 ; 20-C=O-*20a-OH;
Δ1 3
3-C=0—3/3-OH; 4/3,5/3-oxido-> 4/3,5a-diol
3-OPr->3-OH
3-OAc - 3-OH
3 - O A c ^ 3-OH; 17-C=0-*17/3-OH
3-OPr-*3-OH
3 - O P r ^ 3 - O H ; 1 7 - C = 0 ^ 1 7 / 3 -OH
REF.
C-83; C-89
C-83; C-89
C-83
C-88; C-90
C-88
C-88
C-88; C-90
C-83
C-87
C-87
C-90
C-87; C-90
M-539
M-539
M-539
M-539
M-539
TABLE I I I
T ransformat ions by Genus: SACCHAROMYCES
595
SPECIES
ce rev i s i ae (bakers yeast)
SOURCE
Kaiser Wihelm Inst. , Ber l in
IPB
Max Planck Inst, for
Biochem. , München
SCH
SUBSTRATE
3-hyd roxy -1 ,3 ,5 (10 ) - e s t r a t r i en -17-one butyra te
3α, 5α - cy cloandr ostane - 6 ,17-dione
3/3-hydroxy-5-androsten-17-one aceta te
17/3-hydroxy-5a- l -andros ten-3-one
5α-1 -andros tene -3 ,17-d ione
4 -andros tene -3 ,17-d ione
5a -1 -p regnene-3 ,20-d ione
5 a - l - c h o l e s t e n - 3 - o n e
4 -andr ostene -3 ,17 -dione
1,4 -androstadiene -3 ,17 -dione
3 -hyd roxy -1 ,3 , 5 (10) -es t ra t r i en -17-one
5a -andros tane -3 ,17-d ione
3/3-hydroxy-5-androsten-17-one
4 -andros t ene -3 ,17 -d ione
4 -andr ostene - 3 , 1 1 , 1 7 - t r ione
1,4,9(1 l ) - a n d r o s t a t r i e n e - 3 , 1 7 -dione
3,12-diketo-5/3-cholanic acid
5a-cho les tan-3-one
REACTION
3-Oßu - 3-OH
3-OBu — 3-OH; 1 7 - C = 0 - > 17/3-OH
17-C = 0-17/3-OH
17-C=0-17 /3-OH
Δ1— H; 3 - C = 0 — 3/3-OH
1 7 - C = 0 -17/3-OH
Δ ' - Η ; 1 7 - C = 0 -17/3-OH; 3-C = 0 -3/3-OH
A 4 -5 /3 -H;3 -C = 0 - 3 a - O H ; 1 7 - C = 0 -17/3-OH
-
-
1 7 - C = 0 — 17/3-OH
1 7 - C = 0 -17/3-OH
1 7 - C = 0 -17/3-OH
3-C = 0 - 3 / 3 - O H ; 17-C = 0 -17/3-OH
1 7 - C = 0 -17/3-OH
1 7 - C = 0 -17/3-OH
1 7 - C = 0 -17j3-OH
1 7 - C = 0 -17/3-OH
3 - C = 0 - 3 a - O H
3-C=0—3/3-OH
R E F .
M-539
M-539
B-81
M-539
B-80
ß - 7 8
B-80
S-808
B-80
B-80
C-106
D-143
S-806
M-543
M-543
M-543
H-385
G-308
M-543
M-543
596
TABLE I I I
T r a n s f o r m a t i o n s by Genus : SACCHAROMYCES
SPECIES
cerev is iae (compressed yeast)
(pressed yeast)
(mailand-flockige fermente)
SOURCE
ATCC-4125
C
C
I P ß
NG
(Sandoz)
NRRL
SAG
Instituto Pe rez ion -amento
SUBSTRATE
15/3-hydroxy-4-androstene-3,17-dione
3/3-hydroxy-16,17-oxido-5a-pregnan-20-one
16a- methyl -1 ,4 ,9(11) -andros ta -t r i ene -3 ,17 -d ione
3 - h y d r o x y - l , 3 , 5 (10) -es t ra t r ien-17-one
d, 1-3-hydroxy-l , 3 , 5(10)-es t ra -t r i en-17-one
4 -andros tene-3 ,17-d ione
3-keto-5ß-cholanic acid
3,6-diketo-5/3-choianic acid
3/3, 6/3, 8/3,14/3-tetrahydroxy-4, 20, 22-Dufatrienoiide 6-acetate 3-giucoside
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
12/3-hydroxy-4-androstene-3 ,17-dione
5a -androstane -3 ,17-dione
3/3-hydroxy-5-androsten-17-one
4-androstene -3 ,17-dione
5-andros tene-3 ,17-d ione
5a - cholestan - 3-one
REACTION
17-C = 0 -17/3-OH
16,17-oxide-* 16a -OH; 13/3 -Me ->17/3-Me; 20-C = 0—20a-OH; Δ13
1 7 - C = 0 -17/3-OH
17-C = 0 -17/3-OH
d , l - 1 7 - C = 0 -d-17/3-OH + 1-17-C = 0
1 7 - C = 0 -17/3-OH
-
3 - C = 0 -3a-OH
—
-
-
-
1 7 - C = 0 -17/3-OH
3-C = 0-3/3-OH; 17-C=0-17/3-OH
17-C=0-17/3-OH
17-C=0-17j3-OH
Δ — 5a-H; 3 -C = 0— 3/3-OH;17-C = 0 17/3-OH
no reduction
R E F .
H-382
C-85, C-88
R-775
W-1085
V-1055; vV-1094
H-335; H-337
E-221
E-221
S-936a
M-587
M-587
M-587
R-749
M-551; V-1046
M-549
M-550
M-551
M-550
597
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by G e n u s : SACCHAROMYCLS
SACCHAROMYCODES SANSEVIERIA
(Asco. - Endomycetales) ^Spermatophyta -Lil i if lorae)
SPECIES
cerev is iae (brewers yeast)
(Fleishmann)
el l ipsoideus
i'ragiiis
lactis
pas tor ianus
SACCHAROMYCODES
ludwigii
SANSEVIERIA (Plant)
zeylanica (cellular extract)
SOURCE
Phys . Chem. Inst. ,
Okayama
P F
NG
ATCC-10022
NRRL
NRRL
ATCC-2366
NRRL
P F
SUBSTRATE
3,12-diketo-5/3-choianic acid
12a -hydr oxy -3 -keto - 5/3 - choianic acid aceta te
11/3,17/3-dihydr oxy-21-methyl -1 ,4 -p regnad iene -3 ,20 ,21 -t r ione
6a,9ö-dif luoro-l l /3,17/3-dihydroxy - 21 - methyl - 1 , 4 - p r egnadiene-3, 20 ,21- t r ione
4 -andros tene -3 ,17-d ione
4 -andros tene-3 ,17-d ione
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
21 -hydroxy-4 -p regnene -3 ,20 -dione
Sarsasapogenin
Diosgenin
4-dehydrotigogenone
17/3-hydr oxy-4-andros ten - 3-one
1 la, 21 -d ihydroxy-4-pregnene-3,20-dione
REACTION
3 - C - O - 3 a - O H
3-C = 0 ->3a-OH
2 l - C = 0 - 2 1 - O H
2 1 - C = 0 - 2 1 - O H
17-C = 0 -17/3-OH
17-C = 0 -17/3-OH
1 7 - C = 0 - * 17/3-OAc
-
-
-
-
-oxidation -produc ts not identified
-
-
-
1
Δ 1
Δ
Δ4 - 5/3-H
R E F .
K-441
K-442
Α-6
Α-6
Α-17
Μ-572
Μ-572
Μ-587
Μ-587
Μ-587
Μ-587
Μ-587
Μ-587
Η-328
Μ-587
Μ-587
Μ-587
N-658a
N-658a
N-658a
598
I A B L L I I I TAXONOMY
SARCINA (Schizo. - Eubacter ia les) T r a n s f o r m a t i o n s by G e n u s : SARCINOMYCES (imperf. - Monmaies)
SCENEDESMUS (Chlorphyta - Chlorococcales) SCHIZOPHYLLUM (Basidio. - Agaricales)
SPECIES
SARCINA
albida
(in mixed cul ture with Mycococcus sp. Ax)
albiden
aurent iace
lutea
(in mixed culture with Mycococcus sp. A J
marginata
var iabi l i s
SARCINOMYCES
c rus taceum
SCENEDESMUS (Algae)
species
SCHIZOPHYLLUM
commune
SOURCE
IFO(3063)
IAM
IAM
IAM (PCI-1001)
IFO (3232)
NG
NRRL
IAM
IAM
FRI
SCH (J9-A-21)
IAM
SUBSTRATE
11/3,17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
11/3, 17α, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-dione
5-cholesten-3/3-ol (sole carbon source)
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
17a, 21 -d ihydroxy-4 -p regnene-3,20-dione
17a, 21-dihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
REACTION
-
l l a - O H
11a-OH
-
-
—
-
-
-
-
l l a - O H
-
6/3-OH
l l a - O H ; 11/3-OH
-
R E F .
1-428
1-428
S-849
S-849
S-849
1-428
1-428
T-1030
M-587
M-587
M-587
S-849
S-849
S-849
L-527
L-527
S-849
599
T A B L E I I I TAXONOMY
T r a n s f o r m a t i o n s bV G e n u s · SCHIZOSACCHAROMYCES (Asco. - Endomycetales) y ' SCLEROTINIA (Asco. - Helotiales)
SPECIES
SCHIZOSACCHARO-MYCES
octosporus
SCLEROTINIA
alii i
fructicoia
fluctigena
l ibert iana
SOURCE
NRRL
TNAES
C
TNAES
IAM
S
SUBSTRATE
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
17a -hydroxy- l , 4 -p regnad iene -3 ,11 ,20 - t r ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17o ,21-d ihydroxy-4-pregnene-3,20-dione
4-pregnene-3 ,20-d ione
17û-hydroxy-4-pregnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione aceta te
11/3, 21-d ihydroxy-4-pregnene-3,20-dione
REACTION
---
-
21-OH
21-OH
-
2/3-OH; 11/3-OH
2/3,15/3-DIOH
2/3,X-DIOH
products of un-known or questionable s t ruc tu re
2/3-OH
l l a - O H
15/3-OH
2ß,15/3-DIOH
2/3,15ß-DIOH; 21-OAc-*21-OH
2/3-OH
15/3-OH
R E F .
M-587
M-587
M-587
S-849
W-1101
W-1101
S-849
S-849
S-849; S-850; S-859; T-983
T-983
T-983
S-849, S-859; T-983
S-849; S-859; T-983
S-850; T-983
S-849
S-840; S-849, S-853
S-840; S-849 S-853
S-840; S-849; S-853
600
T r a n s f o r m a t i o n s by Genus:
TABLE I I I
SCLEROTINIA SCLEROTIUM
TAXONOMY
(Imperf. - Mycelia Steri l ia)
SPECIES
libertiana
sc le ro t io rum
SCLEROTIUM
coffeicolum
hydrophilum
SOURCE
S
TNAES
FAHU
S
OR
NARI
S
SUBSTRATE
17a, 21 -dihydroxy-4-pregnene-3,20-dione
17a,21 -dihydroxy -4 -pr egnene -3,20-dione
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
17/3-hydroxy-17a-propyl-4-andros ten-3-one
17a, 21-dihydroxy-4-pregnene -3,20-dione
4-pre gnene-3 ,20-dione
17a-hydroxy-4-pregnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
21-hydroxy-4-p regnene-3 ,20-dione aceta te
REACTION
2/3-OH
11a-OH
11/3-OH
X-OH
2/3-OH; 11/3-OH
2]3-OH; 11/3-OH
2/3-OH
11a-OH
llj3-OH
16/3-OH
6/3-OH; l l a - O H
6/3,1 l a -DIOH
6/3-OH
l l a - O H
6/3-OH; l l a - O H
6/3-OH; 2 1 - O A c -21-OH
l l a - O H ; 21-OAc — 21-OH
R E F .
S-849; S-859; S-860; T-983
S-849; S-859; S-860
S-849; S-859; S-860
T-983
S-849
S-849
S-860
S-860
S-860
S-950
S-849
S-849; S-856; S-859
S-856; S-859
S-849; S-856; S-859
S-856
S-856
S-856
TABLE I I I
TAXONOMY
Transformat ions by Genus: SCLEROTIUM SCOPULARIOPSIS (Imperf. - Moniliales)
601
SPECIES
hydrophilum
(var. i r r egu la r i s )
rolfs i i
SCOPULARIOPSIS
1 amer icana
1 brevicaul is
SOURCE
S
CBS QM-93-A
ATCC-12450
FRI
NRRL-1103
SUBSTRATE
21-hydroxy-4 -p regnene -3 ,20 -dione ace ta te
11/3,21-dihydroxy-4-pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17/3-hydroxy-4-androsten-3-one
4 -p regnene-3 ,20-d ione
17ö, 21 -dihydroxy -4 -p r egnene -3,20-dione
17/3-hydroxy-4-androsten-3-one
4 -p regnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a ,21-d ihydroxy-4- p r egnene -3, 20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
4 -p regnene-3 ,20-d ione
REACTION
6/3, l la-diOH; 2 1 - O A c -21-OH
6/3-OH; 11/3-OH-*
n-c=o 15/3-OH; 11/3-OH —
n-c=o 6/3-OH
11a-OH
l l a - O H ; 11/3-OH
l l a - O H ; 11/3-OH
1ξ-OH; l l a - O H ; llj3-OH; 1 1 -C = 0 (via 11/3-OH)
1|-OH; l l a - O H ; 11/3-OH; 1 1 -C = 0 ( via 11/3-OH)
1ξ-OH; l l a - O H ; 11/3-OH; 1 1 -C = 0 (via 11/3-OH)
Ιξ-OH; l l a - O H ; 11/3-OH; 1 1 -C = 0 (via 11/3-OH)
Ιξ-ΟΗ; l l a - O H
l l a , 1 7 a - d i O H
R E F .
S-856
S-849; S-856
S-856
S-849; S-856; S-859
S-849; S-856; S-859
C-313
G-313
G-313
G-313
G-313
G-313
G-313
S-849
D-188
602
T r a n s f o r m a t i o n s by Genus:
TABLE I I I
SCOPULARIOPSIS SEPEDONIUM SEPTOMYXA
TAXONOMY
(Imperf. - Moniliales) (Imperf. - Melanconiales)
SPECIES
brevicaul is
SEPEDONIUM
ampul losporum
SEPTOMYXA
aescul i
SOURCE
NRRL
NRRL-2877
PH
PH
U
SUBSTRATE
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
5 /3 -p regnane -3 , l l , 20 - t r i one
l l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
r e t r o - 4 - p r e g n e n e - 3 , 2 0 - d i o n e
£e t ro_-4 ,6 -p regnad iene-3 ,20-dione
17/3 -hydr oxy - r e t r o - 4 -andr osten -3-one
r e t r o - 4 , 6 - p r e g n a d i e n e - 3 , 2 0 -dione
17/3-hydroxy-19-nor-4-androsten-4 -es t rone
17/3-hydroxy-4-androsten-3-one
17j3 -hydr oxy -1 la - methyl -4 -andros ten-3-one
11/3,17/3-dihydr oxy -17a -methyl -4-andros ten -3-one
4 -andros tene -3 ,17 -dione
5a -p regnane -3 ,11 ,20 - t r i one
REACTION
—
—
~
16a-OH
17a-OH
16a-OH
16a-OH
16a-OH
16a-OH
Δ1; enoL
Δ ; enol. ; 17/3-OH ^ 1 7 - C = 0
Δ1
Δ1; 17/3-OH^ 1 7 - C = 0
Δ1
Δ1
Δ 1
Δ1; 1 7 - C = 0 ^ 17a-oxa-17-C =o Δ1; 1 7 - C = 0 -170-OH
Δ1; 1 7 / 3 - A c -1 7 - C = 0
REF.
M-587
M-587
M-587
F-252
M-646
P - 7 3 5
P - 7 3 5
P - 7 3 5
P - 7 3 5
W-1072
W-1072
W-1072
W-1072
W1072
E-206
W-1072
W-1072
W-1072
W-1072
chrysospermum
TABLE I I I
603
T r a n s f o r m a t i o n s by Genus: SEPTOMYXA
SPECIES
aescul i
SOURCE
U
SUBSTRATE
4-pregnene-3 ,20-d ione (use of washed mycel ium and var ious addit ives changes proport ion of products)
1 l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
11/3-hydroxy-4-pregnene-3,20-dione
17a -hydroxy-4 -p regnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17ce, 21 -dihydroxy-4-pregnene -3,20-dione
1 1/3, 17a, 21 - t r ihydroxy -4 - p r e g -nene -3 ,20-d ione
l l / 3 ,17a ,21 - t r i hyd roxy-6a -methy l -4 -p regnene-3 ,20-d ione
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
REACTION
Δ1
Δ1; 17/3-Ac — 17ß-OH
Δ1; 17 /3 -Ac-1 7 - C = 0
Δ1; 17/3-Ac — 17a-oxa-17-C =o
Δ1
Δ1; 17 /3 -Ac-17/3-OH
Δ1; 17/3-Ac-» 1 7 - C = 0
Δ1; 17/3-Ac-» 17/3-OH
Δ1; 1 7 / 3 - A c -1 7 - C = 0
Δ1
Δ1; 17»-OH-17/3-Ac--17/3-OH
1
Δ
Δ1; 17/3-(20-C = 0 - 2 1 - O H ) -17/3-OH
Δ1; 17/3-(20-C = 0 - 2 1 - O H ) -1 7 - C = 0
Δ1; 17/3-(20-C = 0 - 2 1 - O H ) -17a-oxa-17-C =o
Δ1
Δ1
1
Δ
Δ 1
R E F .
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
604
TABLE I I I
T r a n s f o r m a t i o n s by Genus: SEPTOMYXA
SPECIES
aescul i
affinis
SOURCE
UC
ATCC-6737
SUBSTRATE
4 -pregnene - 3 , 1 1 , 2 0 - t r ione
17a ,21-d ihydroxy-4-pregnene-3 , 1 1 , 2 0 - t r ione
l l /3 ,21-dihydroxy-4 ,17(20)-pregnadien-3 -one
In the following reac t ions the use of one or the other of the fol-lowing " a c c e l e r a t o r s , " "indue er s " or " p r o m o t e r s " will be designated by the s y m -b o l ^ A) under substrate . -
Lis t of Acce le ra to r s
l , 4 -andros tad iene-3 ,17-d ione
17ß-hydroxy- l , 4 -andros t ad i ene -3,17-dione
1 7 a - o x a - D - h o m o - l , 4 - a n d r o s t a -d iene-3 ,17-dione
4 -pregnene-3 ,20-d ione
1Ια-hydroxy-4 -p regnene -3 ,20 -dione
l l /3 ,21-dihydroxy-4 ,17(20)-pr egnadiene -3 ,20 -dione
3 -keto -b i snor -4 -cholen -22 -al
3 -keto -b i snor -4-cholen-22 -ol
3 -keto-bisnor -1 ,4 -choladien-22 -al
3 -keto -bisnor -1 ,4 -choladien-22 -ol
3 -ke to -b i sno r -1 ,4 -choladien-22 -oic acid
17/3-hydroxy-4-estren-3-one
REACTION
Δ1; 17/3-Ac-» 1 7 - C = 0
Δ1; 17 /3 -Ac-17/3-OH
Δ1
Δ1
Δ1; enol.
Δ1; enol. ; 17/3-OH^ 1 7 - C = 0
R E F .
W-1072
W-1072
W-1072
W-1072
B-43; B-44; F-249; F - 2 5 1 ; F -253 ; H-395; L-513; L-517; M-530; M-531; M-532; M-534; M-647; P -709 ; S-833; S-922; S-924; S-925; S-926; S-927
M-573; W-1072
M-573; W-1072
TABLE I I I
605
T r a n s f o r m a t i o n s by Genus : SEPTOMYXA
SPECIES
affinis
SOURCE
ATCC-6737
SUBSTRATE
17/3-hydroxy -2a -methyl -4 -es -t r en -3 -one
17/3-hydroxy-4-methyl -4-es t ren-3-one
17a-ethinyl-6a-f luoro-17/3-hydroxy-4 -es t r en -3 -one
6a-fluoro-17/3-hydroxy-17a-me thy l -4 - e s t r en -3 -one
6α -flu o r o - 17/3-hydroxy- 17α-methy le th iny l -4 -es t ren-3-one
6a - f luo ro -4 -e s t r ene -3 ,17 -d ione
6/3-f luoro-4-es t rene-3 ,17-dione
6 a - f l u o r o - 4 - e s t r e n e - 3 , 1 1 , 1 7 -t r ione
6 /3 - f luoro-4-es t rene-3 ,11 ,17-t r ione
4, 7 - e s t r ad i ene -3 ,17 -dione
1 7/3 -hydr oxy -4 -andr osten -3 -one
2α, 17/3-dihydroxy-4-andr osten -3-one diacetate
2/3,17/3-dihydroxy-4-andr osten -3-one diacetate
17/3-hydr oxy -17a-methyl -4 - an -dr osten -3 -one
17a-brometh iny l -6a- f luoro-4-andros ten-3-one
17α-bromethinyl -17/3-hydr oxy-4-andros ten-3-one
REACTION
Δ1; enol. ; 17/3-OH — 1 7 - C = 0
Δ ; enol. ; 17/3-OH-> 1 7 - C = 0
Δ ; enol.
1
Δ ; enol.
Δ ; enol.
Δ ; enol.
Δ1; enol.
Δ1; enol.
Δ ; enol.
Δ1; enol.
Δ1
Δ1; 17/3-OH — 1 7 - C = 0
Δ1; 17/3-OH -» 17a-oxa-17-C
=o 2a-OAc — 2a-OH; 17/3-OAc -> 17/3-OH
2/3-OAc — 2/3-OH; 17/3-OAc - 17/3-OH
2/3-OAc — 2/3-OH; 17/3-OAc - 1 7 - C = 0
Δ1
Δ1
1
Δ
R E F .
P -731
P-731
C-93
C-93
C-93
P-709
P-709
P-709
P-709
3-72
W-1072
W-1072
W-1072
H-399
H-399
H-399
E-205; W-1072
0 -694 ; 0 -695
0 -694 ; 0 -695
606
TABLE I I I
T r a n s f o r m a t i o n s by G e n u s : SEPTOMYXA
SPECIES
affinis
SOURCE
ATCC-6737
SUBSTRATE
1 la -br omethinyl -17/3 - methoxy -4 -andros ten-3-one
17a-chlorethinyl-17/3-hydroxy-4 -andr osten -3 -one
17a-chlorethinyl-17/3-methoxy-4 -andr osten -3 -one
17a-ethinyl-6a-fluoro-17/3-hydroxy-4 -andr osten -3 -one
1 7α- ethyl -6α -fluor o - l 7/3-hydroxy-4-andros ten-3-one
l l ß , 17/3-dihydroxy- 17α -methyl -4-andros ten -3-one
6a-fluoro-17/3-hydroxy-17a-methyl -4 -andr osten -3 -one
17a -br omethinyl -6a -ch loro-17ß -hydroxy-4-andros ten-3-one
17a-bromethinyl-6a-f luoro-17/3-methoxy-4-andros ten-3-one
17a-bromethinyl-17/3-hydroxy-6a -methy l -4 -andros ten -3 -one
6a-chloro-17a-chlorethinyl-17/3-hydroxy -4 -andr osten -3 -one
17a-chlorethinyl-6a-f luoro-17/3-hydroxy-4 -andr osten -3 -one
17a-chlorethinyl-6a-f luoro-17/3-methoxy-4-andros ten-3-one
17a -chlor ethinyl-17/3- hydroxy -6a-methyl -4 -andr osten -3 -one
9a-fluoro-ll j3,17/3-dihydroxy-17a-methyl -4-andr o s t e n - 3 -one (+A)
6a - f luor o -17/3 - hydr oxy -17a -methy le th iny l -4 -andros ten-3-one
17/3-hydroxy-17a-methyl-9/3,11/3-oxido-4-andros ten-3-one (+A)
6a-f luoro-17/3-hydroxy-4-andro-s t e n e - 3 , l l - d i o n e
4 -andros tene-3 ,17-d ione (testolic acid was not produced by cu l tu res forming lac tone-Ref. H-398)
REACTION
Δ 1
Δ1
Δ1
Δ1
Δ 1
Δ1
Δ1
Δ1
Δ 1
Δ1
Δ 1
Δ 1
Δ1
Δ1
Δ 1
Δ1
Δ1
Δ1
Δ1
R E F .
0 - 6 9 4 ; 0 -695
0 -694 ; 0 -695
0 -694 ; 0 -695
C-93
C-93
E-206
C-93
0 -694 ; 0 -695
0 -694 ; 0 -695
0 -694 ; 0 -695
0 -694 ; 0 -695
0 -694 ; 0 -695
0 -694 ; 0 -695
0 -694 ; 0 -695
M-647
C-93
M- 647
P-709
H-399; W-1072
TABLE I I I
607
T r a n s f o r m a t i o n s by Genus: SEPTOMYXA
SPECIES
affinis
SOURCE
ATCC-6737
SUBSTRATE
4-andr os tene-3 ,17-d ione (testolic acid was not produced by cu l tu res forming lac tone-Ref. H-398)
6a- f luoro- l l /3 -hydroxy-4-andro-s tene-3 ,17-d ione (+A)
6/3-f luoro-l l /3-hydroxy-4-andro-s tene-3 ,17-d ione (+A)
6a -fluor o -4 -andr ostene - 3 , 1 1 , 1 7 -tr ione
17a-oxa-D-homo_-4-androstene-3,17-dione
17a-chlorethinyl-6 -fluor 0-17/3 -hydr oxy -4 ,6 -andr ostadien - 3 -one
17a-chlorethinyl-6-f luoro-17/3-me thoxy -4 ,6 - and ros t ad i en -3 -one
17a -chlor ethiny 1 -17/3 -hydr oxy -6 - m e t h y l - 4 , 6 - a n d r o s t a d i e n - 3 -one
6-chloro-17a-chlorethinyl-17/3-hyd roxy -4 ,6 - and ros t ad i en -3 -one
6-ch loro-17a-ch lore th iny l -17ß-methoxy -4 ,6 -andr ostadien -3 -one
17a-bromethinyl -6-chlor o-17/3-hydroxy -4 ,6 -andr os tadien-3 -one
17a-bromo-6-chloro-17j3-m e t h o x y - 4 , 6 - a n d r o s t a d i e n - 3 -one
17a-bromethinyl-6-f luor 0-17/3-hydroxy-4 ,6 -andr o s t a d i e n - 3 -one
17a-bromethinyl-6-f luor 0-17/3-methoxy - 4 , 6 -andr ostadien - 3 -one
17a-bromethinyl-17/3-hydroxy-6 -me thy l -4 ,6 -and r o s t ad i en -3 -one
REACTION
Δ1; 17 -C=0-> Πβ-ΟΉ
Δ1; 1 7 - C = 0 -17a-oxa-17-C =o
1
Δ
Δ1
Δ1
no tes to l ic acid
1
Δ
Δ1
Δ1
Δ1
Δ1
Δ1
1
Δ
Δ1
Δ1
Δ1
R E F .
W-1072
H-398; W-1072
P-709
P-709
P-709
H-398
0 -694 ; 0 -695
0 -694 ; 0 -695
0 -694 ; 0 -695
0 -694 ; 0 -695
0 -694 ; 0 -695
0 -694 ; 0 -695
0 -694 ; 0 -695
0 -694 ; 0 -695
0 -694 ; 0 -695
0 -694 ; 0 -695
608
TABLE I I I
T r a n s f o r m a t i o n s by Genus: SEPTOMYXA
SPECIES
affinis
SOURCE
ATCC-6737
SUBSTRATE
4 ,7 -andros tad iene -3 ,17-d ione
6a- f luoro-17a-hydroxy-5a-pregnane-3 ,20-d ione
3ß-hydroxy-5a-pregnane-11 ,20-dione 20-cycloethyleneketal (+A)
3j3,17a-dihydroxy-5a-pregnane-11,20-dione 20-cycloethylene-ketal (+A)
3/3,21 - d ihydroxy-5a-pregnane-11,20-dione 20-cycloethylene-ketal (+A)
3/3,17a, 21 - t r ihydroxy-5a -p reg -nane-11,20-dione 20-cyclo-ethy leneketal (+ A)
5a -p regnane -3 ,11 ,20 - t r i one (+A)
6/3-fluoro-3/3, 5a-d ihydroxy-preg-nan-20-one 20-cycloethylene-ketal (+A)
3/3,5a-dihydroxy-6/3-methyl-preg-nan-20-one 20-cycloethylene-ketal (+A)
6a-fluor o -17a-hydroxy - 5/3-preg-nane-3 ,20-d ione
5 ß -pregnane - 3 , 1 1 , 2 0 - t r i o n e (compare with ethyleneketal der ivat ive - Ref. R-251)
5/3-pregnane-3,11,20- t r ione 20-cycloethyleneketal (+A)
3/3-hydroxy-5-pregnen-20-one (+A)
3/3-hydroxy-5-pregnen-20-one 20-cycloethyleneketal (+A)
3/3-hydroxy-5-pregnen-20-one 20-methyl enol ether (+A)
REACTION
1
Δ 1
Δ
Δ ^ β - Ο Η -3-C = 0
Δ ; 3/3-OH — 3 - C = 0
Δ ; 3/3-OH -> 3 - C = 0
Δ ; 3j3-OH — 3 - C = 0
Δ ; 17/3-Ac -» 1 7 - C = 0
Δ1; 3 / 3 - O H -3 - C = 0
Δ1; 3 / 3 - O H -3 - C = 0
1
Δ
oxidized to an-dros tane s e r i e s
Δ1; 1 7 / 3 - A c -1 7 - C = 0
Δ
oxidized to an-dros tane s e r i e s
1 5 4
Δ ; Δ - Δ ; 3 /3 -OH-3-C=0
1 5 4
Δ ; Δ - Δ ; 3/3-ΟΗ — 3 - C = 0
R E F .
Β-72
Β-34
F-251
F-251
F-251
F-251
Ε-207; Μ-573; W-1072
F-251
F-251
Β-34
F-251
Ε-207; Μ-573; W-1072
F-249; F - 2 5 1 ; F-253
F-251
F-251
F-251
TABLE I I I
609
T r a n s f o r m a t i o n s by G e n u s : SEPTOMYXA
SPECIES SOURCE SUBSTRATE REACTION REF.
affinis ATCC-6737 3/3-hydroxy-16ce -methyl - 5 - p r e g -nen-20-one 20-cycloethylene-ketal
4 -p regnene-3 ,20-d ione
[occur rence of tes to l ic acid by cu l tures repor ted to p r o -duce testololactone-Ref. H-398; with spo re s - Ref. S-901; use of washed mycel ium and changing proport ion of products by var ious addit ives-Ref.W-10721
1 l a -hyd roxy -4 -p regnene -3 ,20 -dione
l l ß - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
17a -hydroxy-4 -p regnene -3 ,20 -dione (with s p o r e s -Ref. S-901)
17ö-hydroxy-4 -p regnene-3 ,20-dione ace ta te
Δ1; Δ 5 - Δ 4 ; 3 /3-OH-3 - C = 0
F-251
H-399:
Δ1; 17 /3 -Ac-17/3-OH
Δ1; 17/3-Ac -1 7 - C = 0
Δ1; 1 7 / 3 - A c -17a-oxa-17-c=o
Δ 1
Δ1; 1 7 / 3 - A c -17/3-OH
Δ1; 17/3-Ac-> 1 7 - C = 0
Δ1
Δ1; 1 7 / 3 - A c -17/3-OH
Δ1; 1 7 / 3 - A c -1 7 - C = 0
Δ1
Δ1; 170-OH-17/3-Ac — 17/3-OH
Δ1; 17Q-OH-1 7 / 3 - A c -1 7 - C = 0
Δ1; 170-OH-1 7 / 3 - A c -17a-oxa-17-C =o
S-901; W-1072
S-901; W-1072
S-901; W-1072
H-398; S-901; W-1072
E-208; W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
S-901; W-1072
S-901
S-901
B-36
1
Δ
1
Δ
610
TABLE I I I
T r a n s f o r m a t i o n s by Genus: SEPTOMYXA
SPECIES
affinis
SOURCE
ATCC-6737
SUBSTRATE
21-hydroxy-4 -p regnene-3 ,20-dione (with spo re s -Ref. S-901)
1 la -ethyl -4 -pregnene -3 ,20 -dione (with spores)
dione (with spores)
21 -fluoro -4 -pregnene -3 ,20-dione (with spores)
6 a - f l u o r o - l l a -hydroxy-4 -p reg -nene-3 ,20-d ione
6a-fluoro-11/3-hydroxy -4 - p r e g -nene -3 ,20-dione
6ö- f luoro-17a-hydroxy-4-preg-nene-3 ,20-d ione
6j3-f luoro-l la-hydroxy -4 - p r e g -nene -3 ,20-dione
6/3-fluor o - l 1/3-hydroxy -4 - p r e g -nene -3 ,20-dione
6 /3 , l ia -d ihydroxy-4-pregnene -3,20-dione (+A)
l i a , 17a-dihydroxy-4-pregnene -3,20-dione (+A)
11/3,17a-dihydroxy-4-pregnene-3,20-dione (+A)
REACTION
Δ1
Δ1; 17/3-(20-C = 0-21-OH) — 17/3 -OH
Δ1; 17/3-(20-C = 0 - 2 1 - O H ) ^ 1 7 - C = 0
Δ1; 17/3-(20-C = 0 - 2 1 - O H ) -17a-oxa-17-C =o
Δ1
1
Δ
Δ1; 17/3-(20-C = 0 - 2 1 - F ) -17/3-OH
Δ1; 17/3-(20-C = 0 - 2 1 - F ) - * 1 7 - C = 0
Δ1; 17/3-(20-C = 0 - 2 1 - F ) -17a-oxa-17-C =o
Δ1
Δ1
Δ1
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
R E F .
W-1072
S-901; W-1072
S-901; W-1072
S-901; W-1072
S-901
S-901
S-901
S-901
S-901
C-91
C-91
B-34
C-91
C-91
M-647
M-647
M-647
17û-methyl-4-pr egnene-3,20-
TABLE I I I
611
T r a n s f o r m a t i o n s by Genus: SEPTOMYXA
SPECIES
affinis
SOURCE
ATCC-6737
SUBSTRATE
11/3,21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione (with spo re s - Ref. S-901)
21-fluoro-17a-me thy 1-4-preg-nene-3 ,20-d ione (with spores )
21 -hydroxy-17a -me thy l -4 -p reg -nene-3 ,20-d ione ace ta te (with spores)
6α, 17a-d imethy l -4 -pregnene-3,20-dione
9 a - c h l o r o - l 1/3,21-dihydroxy-4-pregnene-3 ,20-d ione
9 a - f l u o r o - l l ß - h y d r o x y - 6 a -methyl-4 -pregnene -3 ,20-d ione (+A)
l l ß , 1 7 a , 2 1 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione [(+A)- Ref. M-647, reac t ion k ine t ics , washed cells-Ref. C-132, use of dr ied thal i i Ref.-F-231]
6a- isobutyl- l l j3,17a, 21- t r ihy-d roxy-4-p regnene-3 ,20-d ione (+A)
7a -cyano- l l / 3 ,17a ,21 - t r ihydroxy-4-pregnene-3 ,20-d ione
7/3-cyano-11/3,17a,21-trihydroxy-4-pregnene-3 ,20-d ione
6a-f luoro-11/3,17a-dihydroxy-2a-methy l -4 -p regnene-3 ,20-d ione (+A)
REACTION
Δ1; 17/3-(20-C = 0-21-OH)-+ 17/3-OH
Δ1; 17/3-(20-C = 0 - 2 1 - O H ) -1 7 - C = 0
Δ1
Δ1; 17a-OH-17/3-(20-C=O-2 1 - O H ) - 17/3-OH
Δ1; 17a-OH-17/3-(20-C=O-21-OH)-» 17-C = 0
1
Δ
Δ1; 2 1 - O A c -21-OH
Δ1
Δ1; 17ß-(20-C = 0 - 2 1 - O H ) -1 7 - C = 0
Δ1
Δ1
1
Δ
1
Δ
1
Δ
Δ 1
R E F .
S-901
S-901
S-901; W-1072
S-901
S-901
S-901
S-901
S-901
H-399
S-923; S-927
C-132; F - 2 3 1 ; M-647; W-1072
H-395
B-75
ß - 7 5
B-43
612
TABLE I I I
T r a n s f o r m a t i o n s by Genus: SEPTOMYXA
SPECIES
affinis
SOURCE
ATCC-6737
SUBSTRATE
9a-f luoro- l l /3 ,17a-d ihydroxy-6 a - m e t h y l - 4 - p r e g n e n e - 3 , 2 0 -dione (+A)
9a- f luoro- l l /3-hydroxy-6a , 16a-dimethyl -4 -pr egnene -3 ,20 -dione
6a- f luoro- l l /3 ,17a , 21- t r ihy-droxy -4 -pregnene-3 ,20-d ione 21-aceta te [(+A)-Ref. M-530 ,531 ,532 , 647]
6/3-fluoro-11/3,17a, 21 - t r ihy-droxy -4 -pregnene-3 ,20-d ione 21-ace ta te (+A)
6α -hexy 1 -11 β, 17α, 21 - t r ihydr oxy -4 -pregnene-3 ,20-d ione (+A)
l l a , 1 7 a , 2 1 - t r i h y d r o x y - 6 4 -methy l -4 -pr egnene-3 ,20-dione (+A)
11 β, 17a, 21 - t r ihydroxy - 2a - mettyl 4 -pregnene-3 ,20-d ione (+A-Ref. M-647)
l l / 3 ,17a ,21- t r ihydroxy-6a -methyl-4 -pr egnene -3 ,20-dione (+A-Ref. H-395; S-833; S-922)
l l /3 ,17a ,21- t r ihydroxy-6/3-methy l -4 -pregnene-3 ,20-d ione (+A-Ref. H-395; S-833)
l l / 3 ,17a ,21 - t r ihydroxy-6 -methy lene -4 -pr egnene - 3 , 2 0 -dione
11/3,17a, 21- t r ihydroxy-6a-penty l -4 -pregnene-3 ,20-d ione (+A)
11/3,17a, 21- t r ihydroxy-6a-pheny 1 -4 -pregnene - 3 ,20 -dione (+A)
11/3,17a, 21 - t r ihydroxy-6a - i so -p ropy l -4 -p regnene-3 ,20-d ione (+A)
11/3,15a, 17a, 21 - t e t r ahydroxy-4-pregnene-3 ,20-d ione (+A)
REACTION
Δ 1
Δ 1
Δ1; 2 1 - O A c ^ 21-OH
Δ1; 21-OAc — 21-OH
1
Δ
1
Δ
Δ 1
Δ 1
1
Δ
1
Δ
1
Δ
1
Δ
Δ 1
Δ 1
R E F .
L-513
S-923
H-396; M-530; M-531; M-532; M-647; S-924; S-926
S-925; S-926
H-395
S-833
H-394; M-573; M-647
H-395; L-512; M-573; M-647; S-833; S-922; W-1072
H-395; L-512; S-833
F-264
H-395
H-395
H-395
B-44
TABLE I I I
613
T r a n s f o r m a t i o n s by G e n u s : SEPTOMYXA
SPECIES
affinis
SOURCE
ATCC-6737
SUBSTRATE
11/3,15/3,17a, 21 - t e t r ahydroxy-4 -pregnene-3 ,20-d ione (+A)
9a -b r omo-6a-f luoro-11/3,17α-dihy dr oxy-2α-methy l -4 -pr eg-nene-3 ,20-d ione (+A)
9a-bromo-6/3-f luoro- l l /3 , 17a, 21- t r ihydroxy-4-pregnene -3,20-dione 21-ace ta te
9a-chloro-6a-f luoro-11/3 ,17a-dihy droxy- 2a -methyl -4 -pr eg-nene -3 ,20-dione (+A)
9a-chloro-6/3-fluoro-11/3,17a, 2 1 -t r i h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione 21-aceta te
6a-fluoro-11/3,17a, 21 - t r ihydroxy J 2 a - m e t h y l - 4 - p r e g n e n e - 3 , 2 0 -dione (+A)
6a-fluoro-11/3,17a, 21 - t r ihy -d roxy-16a -me thy l -4 -p r eg-nene-3 ,20-d ione 21-ace ta te
6a- f luoro- l l j3 ,17a , 21 - t r ihy-droxy -16β -methyl -4 -pr eg-nene -3 ,20-d ione 21-ace ta te
6/3-fluoro-11/3,17a, 21 - t r ihydroxy -2 a - m e t h y l - 4 - p r e g n e n e - 3 , 2 0 -dione (+A)
9a-fluoro-11/3,17a, 21 - t r ihy -droxy -6a -methy l -4-pregnene -3 ,20-dione (+A)
9a-fluoro-11/3,15a, H a ^ l - t e t r a -h y d r o x y ^ - p r e g n e n e - S , 20-dione (+A)
9a-fluoro-11/3,15/3,17a, 21 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione (+A)
6a, 9a -dif luoro -11/3,17a -dihy -dr oxy-2a -me thy l -4 -p r egnene -3,20-dione (+A)
6a ,21-d i f luoro- l l /3 ,17a-d ihy-d roxy-2a -me thy l -4 -p r egnene-3,20-dione (+A)
6 a , 9 a , 2 1 - t r i f l u o r o - l l / 3 , 1 7 a - d i -hyd roxy-4 -p regnene -3 ,20 -dione (+A)
REACTION
Δ1
Δ 1
Δ1; 21-OAc— 21-OH
1
Δ
Δ1; 21-OAc-* 21-OH
Δ 1
Δ1; 2 1 - O A c -21-OH
Δ1; 2 1 - O A c ^ 21-OH
Δ 1
Δ 1
Δ 1
Δ 1
Δ1
Δ1
Δ 1
R E F .
B-44
B-43
S-926
B-43
S-926
B-43
L-517
L-517
B-43
S-921
B-44
B-44
B-43
B-43
M-534
614
TABLE I I I
T r a n s f o r m a t i o n s by Genus: SEPTOMYXA
SPECIES
affinis
SOURCE
ATCC-6737
SUBSTRATE
6/3 ,9a-d i f luoro- l l /3 ,17a ,21- t r i -hydroxy-4 -p regnene -3 ,20 -dione 21-aceta te
l l / 3 ,17a ,21- t r ihydroxy-16a-methyl-6 - mé thy lène -4 -p reg -nene-3 ,20-d ione
11/3,15/3,17a, 21- te t rahydroxy-15a -me thy l -4 -p regnene -3 ,20 -dione (+A)
l l / 3 ,16a ,17a ,21 - t e t r ahydroxy-6 a - m e t h y l - 4 - p r e g n e n e - 3 , 2 0 -dione
9a -b romo-6a ,21 -d i f l uo ro - l l / 3 , 17a-d ihydroxy-2a-methyl -4-pregnene-3 ,20-d ione (+A)
9 a - c h l o r o - 6 a , 2 1 - d i f l u o r o - l l / 3 , 17a-d ihydroxy-2a-methyl -4-pregnene-3 ,20-d ione (+A)
9a- f luoro- l l j3 ,15 /3 ,17a ,21- te t ra -hydr oxy-15a -me thy l -4 -p reg -nene-3 ,20-d ione
9 a - f l u o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 - t e t r a -hydroxy-6a -me thy l -4 -p reg -nene-3 ,20-d ione
6a, 9a, 21 - t r i f luoro-11/3,17a-di-hydr oxy-2a -methy l -4 -p r eg -3 ,20-dione
4 -pregnene - 3 , 1 1 , 2 0 - t r ione
REACTION
6a - f l uo ro -4 -p regnene -3 ,11 ,20 -t r ione
6 /3-f luoro-4-pregnene-3 ,11,20-t r ione
6a -me thy I -4 -p r egnene -3 ,11 ,20 -t r ione
3 -me thy l -4 -p regnene -3 ,11 ,20 -tr ione
Δ ; 21-OAc-21-OH
Δ1; 17/3-Ac-17/3-OH
Δ1; 17/3-Ac-1 7 - C = 0
Δ1; 17/3-Ac-17/3-OH
Δ1; 17/3-Ac-1 7 - C = 0
Δ1; 17/3-Ac-17/3-OH
R E F .
S-926
F-264
B-44
L-517
B-43
B-43
B-44
L-517
B-43
E-M W
208; -574; -1072
W-1072
W -1072
C-91
C-91
R-780
R-780
R-780
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
TABLE I I I
615
T r a n s f o r m a t i o n s by Genus: SEPTOMYXA
SPECIES
affinis
SOURCE
ATCC-6737
SUBSTRATE
6/3-methyl -4-pregnene-3 ,11 ,20-t r ione
9a -fluoro -6a - methyl -4 -pr egnene -3 ,11 ,20 - t r i one
17a, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r ione (with spo re s -Ref. S-901)
6a- f luoro-17a-hydroxy-2a-m e t h y l - 4 - p r e g n e n e - 3 , l l , 2 0 -t r ione
2a-f luoro-17a, 21-dihydroxy-4-pregnene - 3 , 1 1 , 2 0 - t r ione
6a-f luoro-17a, 21-dihydroxy-4-p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e 2 1 -aceta te (+A)
6ß-f luoro-17a, 21 -d ihydroxy-4-p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e 21-aceta te (+A)
9a-f luoro-6a , 16a-d imethyl -4-p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
17a, 21 -d ihydroxy-6a-methyl -4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e ( + A-Ref. L-512)
17a,21-dihydroxy-6/3-methyl-4-p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
15a, 17a, 21 - t r i hyd roxy-4 -p reg -nene - 3 , 1 1 , 2 0 - t r ione
15/3,17a, 21 - t r i hyd roxy-4 -p reg -n e n e - 3 , 1 1 , 2 0 - t r i o n e
9a-bromo-6a- f luoro-17a-hydroxy-2 a - m e t h y l - 4 - p r e g n e n e - 3 , 1 1 , 20- t r ione (+A)
9a-bromo-6 /3- f luoro-17a ,21-d ihyd roxy-4 -p regnene -3 ,11 , 20- t r ione 21-aceta te
REACTION
Δ1; 17j3-Ac-* 1 7 - C = 0
Δ 1
Δ 1
Δ1; 17α-ΟΗ-17/3-(20-C = O-2 1 - O H ) - 17ß-OH
Δ1; 17α-ΟΗ -17/3-(20-C = O-2 1 - O H ) -1 7 - C = 0
1
Δ
Δ 1
Δ1; 21-OAc-* 21-OH
Δ ;21-OAc-> 21-OH
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
Δ1; 21 -OAc-» 21-OH
R E F .
R-780
S-923; S-927
S-901; W-1072
S-901
S-901
B-43
H-401
M-530; M-531; M-532; S-924; S-926
S-925; S-926
S-923
L-512; S-833
S-833
ß - 4 4
B-44
B-43
S-926
616
TABLE I I I
T ransformat ions by Genus: SEPTOMYXA
SPECIES
affinis
SOURCE
ATCC-6737
SUBSTRATE
9a-chloro-6a-f luoro-17a-hydroxy-2 a - m e t h y I - 4 - p r e g n e n e - 3 , l l , 20- t r ione (+A)
9a - chlor o - 6/3 -fluor o -17a, 21 -di -hyd roxy-4 -p regnene -3 ,11 , 20- t r ione 21-aceta te
6a- f luoro-17a ,21-d ihydroxy-2a-m e t h y l - 4 - p r e g n e n e - 3 , 1 1 , 2 0 -tr ione (+A)
6/3-fluoro-17a, 21 -dihydroxy-2a-m e t h y l - 4 - p r e g n e n e - 3 , 1 1 , 2 0 -t r ione (+A)
9a - f luoro -15a ,17a ,21- t r ihydroxy-4 -pr egnene - 3 , 1 1 , 2 0 - t r i o n e ( + A )
9a-f luoro-15/3 ,17a,21- t r ihydroxy-4 -pr egnene - 3 , 1 1 , 2 0 - t r ione (+A)
6a, 9a -dif luor o -17a -hydr oxy - 2a -methyl -4-pr e g n e n e - 3 , 1 1 , 2 0 -t r ione (+A)
6/3,9a-dif luoro-17a,21-dihydroxy-4 -p regnene -3 ,11 ,20 - t r i one 21 -aceta te
6α, 21 -d i f luoro-17a-hydroxy-2a-m e t h y l - 4 - p r e g n e n e - 3 , 1 1 , 2 0 -t r ione (+A)
15/3,17a, 21-trihydroxy-15a-meth5fl -4 -pr egnene - 3 , 1 1 , 2 0 - t r ione (+A)
9a -b romo-6a ,21-d i f luoro -17a-hydroxy-2a -me thy l -4 -p reg -nene -3 ,11 ,20 - t r i one (+A)
9a -ch lo ro -6a , 21 -dif luoro-17a-hydroxy-2a-methy l -4 -pr eg-nene -3 ,11 ,20 - t r i one (+A)
9a-f luoro-15/3 ,17a,21- t r ihydroxy-1 5 a - m e t h y l - 4 - p r e g n e n e - 3 , 1 1 , 20- t r ione (+A)
6a ,9a ,21- t r i f luo ro -17a-hydroxy-2a -methy l -4 -p r egnene-3 ,11 ,20-t r ione
20-methoxy-4,17(20)-pregnadien-3-one
REACTION
1
Δ
Δ 1 ; 2 1 - O A c -21-OH
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
Δ ; 2 1 - O A c - * 21-OH
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
1
Δ
R E F .
B-43
S-926
B-43
B-43
ß-44
B-44
B-43
S-926
B-43
B-44
B-43
B-43
B-44
B-43
E-251
TABLE I I I
Transformat ions by Genus: SEPTOMYXA
617
SPECIES
affinis
SOURCE
ATCC-6737
ATCC-13425
SUBSTRATE
11/3,21-dihydroxy-4,17(20)-pr e gnadie n - 3 - one
(use of inc rementa l addition for de hydrogénation a t con-cent ra t ions exceeding solubi l -ity of subs t ra te - Ref. C-130, react ion kinet ics and use of washed cel ls - Ref. C-132 , continuous t ransformat ion -Ref. R-766 (+A) -Ref . M-647)
6a - fluor o-11/3,21-dihydroxy -4 , 17(20) -pregnadien-3 -one 21-aceta te (+A)
11/3,21 -d ihydroxy-2a-methy l -4 , 17(20)-pregnadien-3-one
11/3,21 -d ihydroxy-6a-methy l -4 , 17(20) -pregnadien-3-one
11/3,16a, 21 - t r ihydroxy-4 ,17(20) -cis -pregnadien-3-one 2 1 -aceta te
11/3,21 -dihydroxy-6a, 16a -d i -methyl -4 ,17(20)-pregnadien-3-one (+A)
l l /3 ,21-dihydroxy-6a,16/3-di-methyl-4,17(20) -pregnadien-3-one (+A)
6 ,17a -d ime thy l -4 ,6 -p regnad iene -3,20-dione (with conidia)
l l / 3 , 17a ,21 - t r i hyd roxy -6 -methy l -4 ,6 -pr egnadiene - 3 , 20-dione (+A)
17a, 21 -d ihydroxy-6 -me thy l -4 ,6 -p r e g n a d i e n e - 3 , l l , 2 0 - t r i o n e (+A)
1 l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione (demonstrat ion of indueible enzyme- Ref. K-456)
11/3,17a, 21 - t r ihydroxy-4 - p r e g -nene-3 ,20-d ione (see note above)
l l j ß ,17a ,21 - t r ihydroxy-6a -methy l -4 -p regnene-3 ,20-d ione (see note above)
REACTION
1
Δ
Δ ; 2 1 - O A c - » 21-OH
1
Δ
1
Δ
Δ 1
Δ1
1
Δ
Δ 1
1
Δ
Δ 1
1
Δ
1
Δ
Δ 1
REF.
C-130; C-132; M-647; R-766; S-922; W-1072
L-517
H-394; M-573; S-927
M-573; S-928
M-529
L-517
L-517
S-901
H-395
H-395
K-456
K-456
K-456
618
TABLE I I I
Transformat ions by Genus: SEPTOMYXA
SPECIES
affinis
corni
SOURCE
ATCC-13425
AY
ATCC-13416 CBS
SUBSTRATE
17a ,21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione (see note above)
11)3,21 -dihydroxy-4,17(20) -p reg -nadien-3-one (see note above)
17ß-hydroxy-4-andros tene -3 ,17-dione (with conidia)
4 -pregnene-3 ,20-d ione (with conidia)
17a, 21 -dihydroxy -4 -pr egnene - 3 , 20-dione (with conidia)
l l a , 1 7 a , 2 1 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
17/3-hydroxy-4-estren-3-one
17/3-hydroxy-4-androsten-3-one
17/3-hydroxy-17a-methyl-4-andros ten-3-one
11/3,17/3 -dihydroxy -17a -methyl -4 -andros ten-3-one
4 -andros tene-3 ,17-d ione
5a -pre gnane -3 ,11 ,20 - t r ione
4 -pregnene-3 ,20-d ione • (use of washed mycel ium and
var ious addit ives changes p r o -port ion of products)
REACTION
Δ1
Δ 1
Δ 1 · 17j3-OH-+ 1 7 - C = 0
X
Δ
1
Δ
1
Δ
Δ1; enol.
Δ ; enol. ; 17/3-OH^ 1 7 - C = 0
1
Δ
Δ1; 17/3-OH^ 1 7 - C = 0
Δ1
1
Δ
Δ 1
Δ1; 1 7 - C = 0 -17a-oxa-17-C
=o Δ1; 17 -C=0-> 17/3-ΟΗ
Δ1; 17/3-Ac-» 1 7 - C = 0
Δ1
Δ1; 17/3-Ac — 17/3-OH
Δ1; 17/3-Ac^ 1 7 - C = 0
R E F .
K-456
K-45 6
S-835
S-835; V-1048
S-835; V-1048
S-835
W-1072
W-1072
W-1072
W-1072
W-1072
E-206
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
TABLE I I I
619
T r a n s f o r m a t i o n s by Genus: SEPTOMYXA
SPECIES
corni
SOURCE
ATCC-13416 CBS
SUBSTRATE
4-pregnene-3 ,20-d ione (use of washed mycel ium and var ious addit ives changes p r o -port ion of products)
1 l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
l l / 3 -hydroxy-4 -p regnene -3 ,20 -dione
17a -hydroxy-4 -p regnene -3 ,20 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a ,21-d ihydroxy-4-p regnene-3 , 20-dione
11/3,17a, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
11/3,17a, 21 - t r ihydroxy-6a-methy l -4 -p regnene-3 ,20-d ione
4 - p r e g n e n e - 3 , 1 1 , 20-tr ione
REACTION
Δ1; 17/3-Ac-> 17a-oxa-17-C =o
Δ1
Δ1; 17 /3-Ac^ 17/3-OH
Δ1; 17/3-Ac — 1 7 - C = 0
Δ1· 17ß-Ac-> 17/3-OH
Δ1; 17/3-Ac-+ 1 7 - C = 0
Δ1
Δ1; 17α-OH-17/3-Ac^ 17/3-OH
1
Δ
Δ1; 17j3-(20-C = 0-21-OH) -17/3-OH
Δ1; 17/3-(20-C = 0-21-OH) -» 1 7 - C = 0
Δ1; 17ß-(20-C = 0-21-OH) -» 17a-oxa-17-C =o
1
Δ
1
Δ
1
Δ
Δ1
Δ1; 17/3-Ac ^ 1 7 - C = 0
Δ1; 17/3-Ac^ 17/3-OH
R E F .
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
TABLE I I I
Transformat ions by Genus.· SEPTOMYXA
SPECIES
corni
sal ic ina
SOURCE
ATCC-13416 CBS
U
SUBSTRATE
17a, 21 -d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione
l l ß , 21-dihydroxy-4,17(20)-pregnadien-3 -one
17ß-hydroxy-4-es t ren-3-one
17ß-hydroxy-4-andros ten-3-one
17ß-hydroxy-17a-methyl -4-andros ten-3-one
1 I ß , 17ß-dihydroxy- 17α -methyl -4 -andros ten-3-one
4 -andr ostene -3 ,17 -dione
5a -pregnane - 3 , 1 1 , 2 0 - t r ione
4 -pregnene-3 ,20-d ione (use of washed mycel ium and var ious addit ives changes proport ion of products)
11a -hydroxy-4 -p regnene-3 ,20-dione
l l ß - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
REACTION
Δ 1
Δ 1
Δ ; enol.
Δ ; enol. ; 17ß-OH — 1 7 - C = 0
Δ 1
Δ1; 1 7 β - Ο Η -1 7 - C = 0
1
Δ
Δ1
Δ 1
Δ1; 1 7 - C = 0 -17a-oxa-17-C
=o Δ1; 17-C = 0 -> 17ß-OH
Δ1; 17ß-Ac-* 1 7 - C = 0
Δ1
Δ1; 1 7 ß - A c -17ß-OH
Δ1; 1 7 ß - A c -1 7 - C = 0
Δ1; 17ß-Ac — 17a-oxa-17-C
=o Δ1
Δ1; 1 7 ß - A c -17ß-OH
Δ1; 17ß-Ac-> 1 7 - C = 0
Δ1; 1 7 ß - A c ^ 17ß-OH
R E F .
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
E-206
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
620
SPECIES
sal icina
1 tulasnei
SOURCE
U
SUBSTRATE
l l / 3 -hydroxy-4 -p regnene -3 ,20 -dione
17«-hydroxy-4-p regnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
l l j 3 ,17o ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
l l j 3 ,17a ,21- t r ihydroxy-6a -methy 1-4-pr egnene - 3 ,20-dione
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
17«, 21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r i one
l l /3 ,21-d ihydroxy-4 ,17(20) -preg-nadien-3-one
17/3-hydroxy-4-es t ren-3-one
17/3-hydroxy-4-androsten-3-one
REACTION
Δ1; 1 7 / 3 - A c -1 7 - C = 0
Δ1
Δ1; 17a-OH-17/3-Ac-* 17/3-OH
Δ1
Δ1; 17/3-(20-C= 0-21-OH)-> 17/3-OH
Δ1; 17/3-(20-C = 0 -21-OH)-> 1 7 - C = 0
Δ1; 17/3-(20-C = 0 -21-OH)-+ 17a-oxa-17-C =o
Δ1
1
Δ
1
Δ
1
Δ
Δ1; 17 j3 -Ac-1 7 - C = 0
Δ1; 1 7 / 3 - A c -17/3-OH
Δ1
1
Δ
Δ1; enol.
Δ1; enol. ; 17/3-OH-* 1 7 - C = 0
Δ 1
Δ1; 17/3-OH — 1 7 - C = 0
R E F .
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
T r a n s f o r m a t i o n s by G e n u s :
TABLE I I I
SEPTOMYXA
621
TABLE I I I
Transformat ions by Genus: SEPTOMYXA
SPECIES
tulasnei
SOURCE
U
SUBSTRATE
1 7/3 - hydr oxy -17a - methyl - 4 -andros ten-3-one
11/3,17j3-dihydroxy-17a-methyl-4 -andros ten-3-one
4 -andr ostene -3 ,17 -dione
5 a - p r e g n a n e - 3 , l l , 2 0 - t r i o n e
4 -pregnene-3 ,20-d ione (use of washed mycel ium and var ious addit ives changes propor t ion of products)
1 l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
1 Iß -hyd roxy-4 -p regnene -3 ,20 -dione
17a -hydroxy-4 -p regnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
REACTION
Δ1
1
Δ
Δ 1
Δ1; 1 7 - C = 0 -17a-oxa-17-C = 0 î
Δ1; 1 7 - C = 0 -17/3-OH
Δ1; 1 7 / 3 - A c -1 7 - C = 0
Δ 1
Δ1; 1 7 / 3 - A c -17/3-OH
Δ1; 1 7 / 3 - A c -1 7 - C = 0
Δ1; 1 7 / 3 - A c -17a-oxa-17-C =o
Δ 1
Δ1; 1 7 / 3 - A c -17/3-OH
Δ1; 1 7 / 3 - A c -1 7 - C = 0
Δ1; 17jS-Ac-> 17/3-OH
Δ1; 17/3-Ac — 1 7 - C = 0
Δ 1
Δ1; 17a-OH-17/3-Ac-> 17/3-OH
1
Δ
Δ1; 17/3-(20-C= 0-21-OH) — 17/3-OH
R E F .
W-1072
E-206
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
622
623
TABLE I I I
TAXONOMY
T r a n s f o r m a t i o n s by Genus: SEPTOMYXA SERRATIA (Schizo. - Eubacteriales)
SPECIES
tulasnei
SERRATIA
m a r c e s c e n s
SOURCE
U
ATCC-13477
IAM (1-2;
1-3; 1-7; 1-9; 1-10)
(2-1 2-2)
(2-3)
(2-5; 2-7)
(2-10)
IFO(3046)
SUBSTRATE
21-hydroxy-4 -p regnene -3 ,20 -dione
17a, 21 -dihydroxy -4 -pr egnene -3,20-dione
l l j 3 , 17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
11/3 ,17a,21- t r ihydroxy-6a-methyl-4 -pr egnene -3,20-dion€
4 -pr egnene - 3 , 1 1 , 2 0 - t r i o n e
17ö, 21 -dihydroxy -4 -pr egnene -3 ,11 ,20 - t r ione
l l j3 ,21-d ihydroxy-4 ,17(20)-preg-nadien-3-one
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
REACTION
Δ1; 17/3-(20-C =0-21-OH) -1 7 - C = 0
Δ1; 17j3-(20-C = 0-21-OH) -17a-oxa-17-C =o
Δ 1
1
Δ
1
Δ
1
Δ
Δ1; 17/3-Ac^ 1 7 - C = 0
Δ1; 17/3-Ac^ 17/3-OH
1
Δ
1
Δ
Δ 1
Δ1
Δ 1
Δ 1
Δ 1
Δ1
2j3-OH
—
2/3-OH
Δ1
Δ1; l l a - O H
R E F .
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
W-1072
T-960
S-849
S-849
S-849
S-849
S-849
S-849
S-849
624
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus.· SERRATIA
SHIYUDAKE SORDARIA
SPHACELOMA SPICARIA
(Taxonomy Unclear) (Asco. - Sphaeriales) (Imperf. - Melanconiales) (Imperf. - Moniliales)
SPECIES
marcescens
(in mixed cul ture with Mycococcus sp. Ax)
plymuthica
SHIYUDAKE
spec ies
SORDARIA
spec ies
SPHACELOMA
species
SPICARIA
s impl ic i s s ima
species
violacea
SOURCE
IFO (3046)
IFO (3048)
NG
ATCC-13478
S
NRRL
TNAES
ATCC-13595
LED(Z-118)
NRRL
NRRL
SUBSTRATE
11/3,17a, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
5-cholesten-3/3-ol (sole carbon source)
24 /3-methyl -5 ,7 ,22-choles ta t r ien-3/3-ol (sole carbon source)
11/3,17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
plant saponins
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -p regnene-3,20-dione
plant saponins
Sarsasapogenin
REACTION
-
-
-
-
—
1
Δ
11a-OH
-
-
15/3-OH
15/3-OH
-
R E F .
1-428
1-428
S-849
S-793c; T-1030
S-793c
T-960
S-849
K-478
S-849
A-9 ; B-58
B-56
K-478
M-587
TABLE I I I TAXONOMY
Transformat ions by Genus: SPICARIA SPONDYLOCLADIUM (Imperf. - Moniliales)
625
SPECIES
violacea
v i r idans
SPONDY LOC L ADIUM
aus t ra l e
1 xylogenum
SOURCE
NRRL
FRI
ATCC-12728
ATCC-12727
SUBSTRATE
Diosgenin
4-dehydr otigogenone
17α, 21 -dihydr oxy -4 -pregnene -3 ,20-dione
17/3-hydroxy-4-androsten-3-one
4 -andros tene -3 ,20-d ione
20-hydroxy-5a-pregnan-3-one
20-hydroxy-5/3-pregnan-3-one
3/3-hydroxy-5-pregnen-20-one
4 -p regnene-3 ,20-d ione
17a -hydroxy-4 -p regnene -3 ,20 -dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
6a- f luoro-17a ,21-d ihydroxy-16-methylene -4 -pregnene - 3 , 2 0 -dione 21-propionate
1,4 -pregnadiene -3 ,20-d ione
17a, 21 -d ihydroxy-1 ,4 -p regnad i -ene-3 ,20-d ione
17/3-hydroxy-4-androsten-3-one
4-andros , tene-3 ; 17-dione
20-hydroxy-5a-pregnan-3-one
20-hydroxy-5/3-pregnan-3-one
3/3-hydroxy-5-pregnen-20-one
4 -p regnene-3 ,20-d ione
17a -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
1,4 -pregnadiene -3 ,20-d ione
17a, 21-dihydroxy - 1 , 4 - p r e g n a -d iene-3 ,20-d ione
REACTION
11a-OH; 11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH; 2 1 - P r ^ 2 1 - O H
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
11/3-OH
R E F .
M-587
M-587
S-849
S-790
S-790
S-790
S-790
S-790
S-790
H-391; S-790
H-391; S-790
A-7
S-790
S-790
S-790
S-790
S-790
S-790
S-790
S-790
S-790
S-790
S-790
S-790
626
T r a n s f o r m a t i o n s by Genus:
TABLE I I I
SPOROBOLOMYCES SPORORMIA
SPOROTRICHUM
TAXONOMY
(Imperf. - Moniliales) (Asco. - Sphaeriales) (Imperf. - Moniliales)
SPECIES
roseum
SPORORMIA
fasciculata
leporina
minima
montana
pol lacci i
SPOROTRICHUM
as té ro ïdes
bombycinum
epigaeum
SOURCE
FRI
PH
PH
NRRL-2475
PH
PH
FRI
ATCC-7139
ATCC-7145
SUBSTRATE
17a ,21-d ihydroxy-4-pregnene-3,20-dione
retro_-4-pr egnene -3 ,20 -dione
r e t r o - 4 -pr egnene - 3 ,20 -dione
4 -pregnene-3 ,20-d ione
l l /3 -hydroxy-4-p regnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
l l /3 ,21-d ihydroxy-4-pregnene-3,20-dione
r e t r o - 4 - p r e g n e n e - 3 , 2 0 - d i o n e
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
1,4 -androstadiene -3 ,17 -dione
5a -andr ostane -3 ,17 -dione
5/3-pregnane -3 ,20-dione (reaction depends on a i r r a t e -low -hvdr oxylation only-high -hydroxylation + side chain cleavage - R e t M-582) a i r r a t e not c r i t i ca l if subs t ra te has no side chain a t C-17)
4 -pregnene-3 ,20-d ione (see note this ref. )
4 -p regnene-3 ,20-d ione 20-cyclo-ethyleneketal
1 l a -hyd roxy -4 -p regnene -3 ,20 -dione
REACTION
17/3-Ac-» 17/3-OH
17/3-Ac-» 17/3-OH
17a-OH
17a-OH
17a-OH
17a-OH
17/3 -Ac — 17/3-OH
17/3-Ac-» 17/3-OH
11a-OH
11a-OH
11a-OH; or 11a-OH; 17/3-Ac-» 17/3-OH
11a-OH; or 11a-OH; 17/3-Ac-+ 17/3-OH
11a-OH
17/3-Ac — 17/3-OH
R E F .
S-849
P-734
P-734
D-182a
D-182a
D-182a
D-182a
P-734
P-734
S-849
M-582
M-582
M-582
M-582
F-251
M-582
TABLE I I I
T ransformat ions by Genus·. SPOROTRICHUM
627
SPECIES
epigaeum
1 gougeroti
sulfur es cens
1 va r . beyman
SOURCE
ATCC-7145
IFO (5982)
ATCC-7159
CBS
U
SUBSTRATE
17a-hydroxy-4 -p regnene-3 ,20-
21-hydroxy-4 -p regnene -3 ,20 -dione
l i a , 21-dihydroxy-4-pregnene -3,20-dione
17a,21 -dihydroxy-4-pregnene -3,20-dione
21-hydroxy-1 ,4 -p regnad iene -3,20-dione (low a i r ra te )
(high a i r ra te )
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21 -d ihydroxy-1 ,4 -p regna-d iene-3 ,20-d ione
5/3 -andr ostane -3 ,17 -dione
17/3-hydr oxy-17a-methy l -4 -andros ten-3-one
17/3 -hydr oxy-1 ,4 -andr ostadien -3-one
17α, 21 -d ihydroxy-4-pregnene-3,20-dione (low a i r ra te )
(high a i r ra te)
3 -keto -bisnor-4 -cholenic acid
22 -hydroxy-bisnor-4 -cholen-3 -one
17/3-hydroxy-17a-methyl-4-andros ten-3-one
17/3-hydr oxy-17a-me thy 1-1,4-andr os tadien-3 -one
17α, 21-d ihydroxy-4-pregnene-3,20-dione
4 -p regnene-3 ,20-d ione
REACTION
17a-OH-17/3-Ac-> 17/3-OH
17/3-(20-C = O-2 1 - O H ) -17/3-OH
17/3-(20-C=O-2 1 - O H ) -17/3-OH
17a-OH-17j3-(20-C=O-21-OH) - 17/3-OH
l i a - O H
l i a - O H ; 17β-(20 -C=O-21-OH) -> 17/3-OH
2 0 - C = O -20/3-OH
2 0 - C = O -20/3-OH
l i a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H ; 17a-OH-17/3-(20-C=O - 2 1 -O H ) - 17β-ΟΗ
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H
l l a - O H ; 17/3-Ac—17/3-OH
R E F .
M-582
M-582
M-582
M-582
M-582
M-582
T-958
T-958
M-582
M-582
„M-582
M-582
M-582
M-582
M-582
M-582
E-205; M-582
M-582
S-831
628
T r a n s f o r m a t i o n s by Genus:
TABLE I I I TAXONOMY
SPQROTRICHUM STACHYBOTRYS (Imperf. - Moniliales)
STACHYLIDIUM (Imperf. - Moniliales)
SPECIES
sulfur escens in sequential f e rmen-tation with Pén ic i l -l ium sp. (initial sub-s t r a t e 4 -p regnene-3,20-dione)
STACHYBOTRYS
spec ies
STACHYLIDIUM 1 (possible synonym -
Vert ici l l ium) bicolor
(in mixed cul ture with Bacil lus sphaer icus A T C C - 7 0 5 5 O 1 ] )
1 theobromae
SOURCE
U
NRRL
NG (Sandoz)
ATCC-12672
FRI
IFO (6647)
S
ATCC-12474
SUBSTRATE
17/3-hydroxy-4-androsten-3-one
plant saponins
3/3,6/3,8/3,14/3-tetrahydroxy-4, 20,22-bufatr ienolide 6 - ace -ta te 3-glucoside
17a, 21 -dihydroxy-4-pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
l l j3 ,21-d ihydroxy-4-pregnene-3,20-dione
14a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
17a -hydroxy-4 -p regnene-3 ,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione 21-aceta te
REACTION
11a-OH
3ß [ l ^ - g l u c o -side]-> 3/3-OH
11/3-OH
l l a - O H ; 11/3-OH
l l a - O H ; 11/3-OH
l l a - O H ; 11/3-OH
11/3-OH
14a-OH
11/3-OH
11/3-OH
11/3-OH
l l a - O H ; 11/3-OH
11/3-OH; 2 1 - O A c ^ 21-OH
R E F .
S-831
K-478
S-936a
D-146
S-849
K-468; K-468
K-468
S-843; S-849
S-843; S-849
S-843; S-849
S-841; S-843; S-849; S-851
S-843; S-849
D-146
D-146
D-146
629
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: STACHYLIDIUM STAGONOSPORA STAPHYLOCOCCUS STAUROPHOMA
(Imperf. - Sphaeropsidales) (Schizo. - Eubacteriales) (Imperf. - Sphaeropsidales)
SPECIES
theobromae
STAGONOSPORA
cur t i s i i
STAPHYLOCOCCUS
albus
aureus (Pyogenes aureus)
STAUROPHOMA
species
SOURCE
AY
CBS
PH
NG (rat cecum)
LAM (FAD-209p)
NG (ra t cecum)
NG
ATCC-14288
SUBSTRATE
4-pregnene-3 ,20-d ione (use of conidia)
1 Ία, 21 -dihydr oxy -4 -pregnene -3,20-dione (use of conidia)
17a, 21 -dihydr oxy -4 -pregnene -3,20-dione (use of conidia)
r e t r o -17j3-hydroxy - 4-andr os ten-3-one
r e t r o - 4 - p r e g n e n e - 3 , 2 0 - d i o n e
retro_-4,6 -pregnadiene- 3 ,20 -dione
3a, 7a, 12a- t r ihydroxy-5ß-cholanic acid
17a, 21-d ihydroxy-4-pregnene-3, 20-dione
3a, 7a, 12a- t r ihy dr oxy - 5/3-cholanic acid
5-choles ten-3ß-ol (sole carbon source)
24ß -me thy l -5 ,7 ,22 -cho l e s t a -trien-3/3-ol
17/3-hydroxy-4-androsten-3-one
4 -andros tene -3 ,17-d ione
4 -p regnene-3 ,20-d ione
REACTION
11a-OH; 14a-OH
14a-OH
l l ß - O H
l i a - O H ; l l ß - O H
16a-OH
16a-OH
16a-OH
-
l l ß - O H
-
-
-
16a-OH
16a-OH
16a-OH
R E F .
S-835; V-1048
S-835; V-1048
S-835
D-146
P-736
P-736
P-736
N-675
S-849
N-675
S-793c; T-1030
S-793c
H-397
H-397
H-397
630
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by G e n u s : STEMPHYLIUM STEREUM
STERIGMATOCYSTIS
(Imperf. - Moniliales) (Basidio. - Agaricales) (Imperf. - Moniliales)
SPECIES
STEMPHYLIUM
botryosum
species
STEREUM
fasciatum
induratum
STERIGMATOCYSTIS
japonica
STIGMINA
platani (in mixed culture with Hendersonia rubra [21-OH] or Tricho-derma nigrovirens [17a-OH])
STREPTOCOCCUS
pyogenes
SOURCE
FRI
Takeda
NG (Sandoz)
NRRL
IFO (9994)
IAM
FRI
MCC
NG
STIGMINA (Imperf - Moniliales) STREPTOCOCCUS (Schizo. - Eubacteriales)
SUBSTRATE
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
4-pregnene-3,20-dione
17a,21-dihydroxy-4-pregnene-3,20-dione
3/3,6j3,8/3, 14/3-tetrahydroxy-4,20(22) -bufatrienolide 6-acetate 3-glucoside
plant saponins
17/3 -hydroxy- 17a -methyl -4 -androsten-3-one
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
4-pregnene-3,20-dione
5-choIesten-3/3-oI (sole carbon source)
REACTION
-
14a-OH
14a-OH
3/3-[lVgluco-s i d e ] ^ 3/3-OH
-
1
Δ
1
Δ
Δ1; 2 0 - C = O -20/3-OH
—
-
11/3-OH
REF.
S-849
N-661
N-661
S-936a
K-478
T-959
T-959
T-959
S-849
S-849
M-566
T-1030
631
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by G e n u s : STREPTOMYCES (Scnizo. - Actinomycetaies)
SPECIES
STREPTOMYCES (occasionally
Actinomyces)
albidoflavus
albidus * (Actinomyces)
a lbosporeus
1 albus
(Rossi-Dor ia)
1 (Actinomyces)
SOURCE
Shionogi
CZAS
ATCC-3003
ATCC-3004, 3351
C
CZAS
NG
NRRL
Shionogi
SSSR (3006)
SUBSTRATE
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
11β, 17α, 21 - t r ihydroxy -4 - p r e g -nene -3 ,20 -dione
4 -p regnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3 ,20-dione
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
11/3,17a, 21 - t r ihydroxy -4 - p r e g -nene -3 ,20-d ione
d , l - l , 3 , 5 ( 1 0 ) - e s t r a t r i e n e - 3 , 17/3-diol
4 -p regnene-3 ,20-d ione
l , 3 ,5 (10) -es t r a t r i ene -3 ,17 i3 -d io l
Sarsasapogenin
Diosgenin
4-dehydr otigogenone
17a, 21-dihydroxy-4-pregnene -3 ,20-dione
l l j 3 , 17a ,21 - t r i hyd roxy -4 -p reg -nenex3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
11/3,17a, 21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - l , 4 -p r egnadiene -3 ,20 -dione
REACTION
20-C=O-> 20/3-OH
2 0 - C = O -20/3-OH
16α-ΟΗ
20-C=O » 20/3-OH
2 0 - C = O -20/3-OH
2 0 - C = O ^ 20/3-OH
2 0 - C = O ^ 20/3-OH
d,l-17/3-OH-> d - 1 7 - C = 0 + 1-17/3-OH
use of osc i l lo -polarographic detection of t r ansf or mations of s t e ro ids
17/3-OH -1 7 - C = 0
-
-
-
20-C=O-> 20/3-OH
2 0 - C = O -20/3-OH
2 0 - C = O -20/3-OH
2 0 - C = O -20/3-OH
2 0 - C = O -20/3-OH
2 0 - C = O -20/3-OH
R E F .
K-470
K-470
V-1060
K-470
K-470
K-470
K-470
W-1102
S-929
W-1082
M-587
M-587
M-587
K-470
K-470
K-458
K-459
K-459
K-459
632
TABLE I I I
Transformat ions by Genus: STREPTOMYCES
SPECIES
albus
annulatus * (Actinomyces)
antibioticus
argenteolus (species ATCC-11009 Ref. F -265 , H-380, P - 7 1 6 , P - 7 1 9 - ident-ified a s argenteolus in Ref. F-267)
*
SOURCE
SSSR
CZAS
ATCC-8663
ATCC-11891
NG
ATCC-11009 SQ (MD-248)
SUBSTRATE
1 7 a , 2 1 - d i h y d r o x y - l , 4 - p r e g n a -d i e n e - 3 , l l , 2 0 - t r i o n e
4 -pregnene-3 ,20-d ione
17a, 21 -dihydroxy-4 -pregnene -3 ,11 ,20 - t r ione
4 -pregnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
11/3, 1 7 Q , 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
11/3,16α, 17α, 21- te t rahydroxy-4-pregnene-3 ,20-d ione
9 a - f l u o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy-6a - methy l -1 ,4 -pregnadiene -3,20-dione
5-cholesten-3/3-ol
24/3-methyl-5 ,7 ,22-choles ta t r ien-3j3-ol
4 -andros tene -3 ,17-d ione
3/3-hydroxy-5-pregnen-20-one
REACTION
2 0 - C = O -20/3-OH
16a-OH
1
Δ
l | - O H
1ξ-OH
1ξ-ΟΗ
1ξ-ΟΗ
Ιξ-ΟΗ
1ξ-ΟΗ
1ξ-ΟΗ
Ιξ-ΟΗ
-
-
16α-ΟΗ
Δ ^ Δ * ; 3/3-ΟΗ - 3 - C = 0
Δ ^ Δ ; 3/3-ΟΗ ^ 3 - C = 0 ; 16α-ΟΗ
R E F .
Κ-459
V-1060
C-125
F-234
F-234
F-234
F-234
F-234
F-234
F-234
F-234
S-793C
S-793C
F-265 ; F-267
F-267; P-710; P -712 ; P-716
F-265; F-267; P -712 ; P-716
TABLE I I I
T ransformat ions by Genus: STREPTOMYCES
633
SPECIES
argenteolus
aureofaciens
SOURCE
ATCC-11009 (SQ-MD-248)
ATCC-10762
SUBSTRATE
4-pregnene-3 ,20-d ione (effect of ant ibiot ics - Ref. P-719 - adaptive enzyme inhibitors - Ref. P-711)
21 -hydroxy-4 -p regnene -3 ,20 -dione
21-hydroxy-4-p regnene-3 , 20-dione ace ta te
17a, 21 -dihydroxy -4 -pregnene -3,20-dione 21-ace ta te
12a- f luoro- l l j3 ,17a ,21- t r ihydroxy -4 -pregnene-3 ,20-d ione
9a - f luo ro - l l /3 ,17a ,21- t r ihydroxy-2f -methy l -4 -pregnene - 3 , 2 0 -dione
12a- f luoro- l l /3 ,17a ,21- t r ihydroxy -1 ,4 -pregnadiene- 3 ,20-dione
9a - f luoro - l l j3 ,17a ,21- t r ihydroxy-2 - methyl -1 ,4 -pregnadiene -3,20-dione
4 -p regnene-3 ,20-d ione
17a, 21 -d ihydroxy-4-pregnene-3, 20-dione
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
9a -f luoro -1 I ß , 17a, 21 - t r ihydroxy -4 -p regnene-3 ,20-d ione
9 a - f l u o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 - t e t r a -hydroxy-4-pregnene-3 ,20-d ione
9a- f luoro- l l /3 ,16a , H a ^ l - t e t r a -h y d r o x y - l ^ - p r e g n a d i e n e - S ^ O -dione
REACTION
16a-OH
2/3,16a-diOH
Δ -*5/3-H; 16a-OH
16a-OH
16a-OH; 21-OAc - 2 1 - O H
16a-OH; 21-OAc - 2 1 - O H ; Δ 4 -5/3-H
2/3-OH; 21-OAc - 2 1 - O H
16a-OH
16a-OH
16a-OH
16a-OH
I f -OH
1ξ-ΟΗ
1ξ-ΟΗ
1ξ-ΟΗ
1ξ-ΟΗ
1ξ-ΟΗ
REF.
F-265; F-267; P - 7 1 1 ; P -716 ; P - 7 1 8 ; P-719
F-267; P -716 ; P-718
F-267; P -716 ; P-718
F-288
F-265; F-267; P-716
F-267
F-265; F-267; P-716
H-380
H-380
H-380
H-380
F-234
F-234
F-234
F-234
F-234
F-234
634
TABLE I I I
T ransformat ions by Genus: STREPTOMYCES
SPECIES
aureofaciens
*
bikiniensis
bobilae
SOURCE
ATCC-10762
NRRL-2209
SQ
ATCC-3309
>
NG
SSSR (11062)
(E-55-LL) Shionogi
SUBSTRATE
3)3,14/3-dihydroxy-5j3-20(22)-cardenolide
3ß-hydroxy-5-pregnen-20-one
4 -p regnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
3j3-hydroxy-5-pregnen-20-one
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
11/3, 17a, 21 - t r ihydroxy -4 -p r eg -nene-3 ,20-d ione
9 a - f l u o r o - l l ß , 17α, 21- t r ihydroxy-4-p regnene-3 ,20-d ione
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - l , 4 -pregnadiene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
l , 3 , 5 ( 1 0 ) - e s t r a t r i e n e - 3 , 1 7 a - d i o l
1 ,3 ,5(10)-es t ra t r iene-3 ,17/3-dio l
3 - h y d r o x y - l , 3 , 5 ( 1 0 ) - e s t r a t r i e n -17-one
17α, 21 -d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4-pregnene -3,20-dione
REACTION
7/3-OH
Δ 5 - Δ 4 ; 3j3-OH - ' 3 - C = 0
6/3-OH
9a-OH
6/3,9a-diOH
9a-OH
Δ -»Δ*; 3/3-OH ->3-C=0
1ξ-ΟΗ
16a-OH
16a-OH
16a-OH
Δ 4 ^ 5 α - Η ; 3 -C=0-3 /3 -OH
1ξ-ΟΗ; 16a-OH
16a-OH
16a-OH
16a-OH
15a-OH
16a-OH
16a-OH
16a-OH
2 0 - C = O -20/3-OH
20-C=O — 20/3-OH
REF.
T-1013
P-712
F-288; P-713
F-288; P-713
P-714
P-715
P-710
F-234
P-745
P-745
P-745
K-471
F-234; P-745
P-745
P-745
V-1060
F-285; F-287
S-935
S-935
S-935
K-458
K-470
aureus 4-pregnene-3,20-dione
C Z A S
WC( 3569, 3676)
TABLE I I I
T ransformat ions by Genus.· STREPTOMYCES
635
SPECIES
bobilae
cal ifornicus
*
celluloflavus
SOURCE
(E-55-LL) Shionogi
Shionogi (5119)
\VC (3312)
AMCY
SUBSTRATE
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
1 7a, 21 -dihydroxy -4 -pr egnene -3 ,20-dione
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
3a-hydroxy-5/3-cholanic acid (sole carbon source)
3o, 7a, 12a-tr ihydroxy-5/3-cholanic acid (sole carbon source)
3a, 7a, 12a-tr ihydroxy-5/3-cholanic acid conjugated with glycine-glycocholic acid (sole carbon source)
3α, 7α, 12a-tr ihydroxy-5/3-cholanic acid conjugated with t aur ine- taurochol ic acid (sole carbon source)
3 ,7 ,12- t r iketo-5/3-cholanic acid (sole carbon source)
3 - h y d r o x y - l , 3 , 5 ( 1 0 ) - e s t r a t r i e n -17-one
4 -andros tene -3 ,17-d ione
4 -p regnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione ace ta te
17a, 21-dihydroxy-4-pr egnene-3,20-dione 21-ace ta te
9a- f luoro- l l j3 ,17a , 21 - t r ihydroxy-4-pregnene-3 ,20-d ione
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - l , 4 -pregnad iene-3 ,20-d ione
9a - f luo ro - l l / 3 ,17a ,21 - t r ihydroxy-1,4 -pregnadiene-3 ,20-d ione
4 -pregnene -3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3, 20-dione
11/3,17a, 21 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
REACTION
20-C=O-> 20/3-OH
20-C=O-> 20/3-OH
2 0 - C = O ^ 20/3-OH
uti l ization
util ization
util ization
util ization
uti l ization
16a-OH
16a-OH
16a-OH
16a-OH; 21-OAc - 2 1 - O H
16a-OH; 21-OAc - 2 1 - O H
16a-OH
16a-OH
16a-OH
l | - O H
1ξ-ΟΗ
l | - O H
R E F .
K-470
K-470
K-470
S-785
H-357; S-784; S-785
S-785
S-785
S-785
L-491
L-491
L-491
L-491
L-491
L-491
L-491
L-491
F-234
F-234
F-234
636
TABLE I I I
Transformat ions by Genus: STREPTOMYCES
SPECIES
celluloflavus
c h a r t r e u s i s
chrysomal lus *
coelicolor
*
dias ta t icus (Krainsky)
1 * I d ias ta tochromogenes
1 endus
1 e ry th reus
exfoliatus
SOURCE
AMCY
Shionogi
CZAS
C
CZAS
WC (3593)
ATCC-3315
AY
CZAS
CZAS
U (9-20)
P F
CZAS
SUBSTRATE
11/3,16α, 17α,21- te t rahydroxy-4-pregnene-3 ,20-d ione
9 a - f l u o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 -t e t r ahydroxy-4 -p regnene -3,20-dione
11/3, 17α, 21- t r ihydroxy-6α-methyl - l , 4 - p r e g n a d i e n e - 3 , 2 0 - d i o n e
17α, 21 -dihydroxy -4 -pr egnene -3 ,20-dione
11/3,17a, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
4-pregnene-3 ,20-d ione
d , l -17a , 21-d ihydroxy-4-preg-
17a, 21-dihydroxy-4-pregnene -3,20-dione
l l / 3 ,17a ,21 - t r i hyd roxy-4 -pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
21-hydroxy-4 -p regnene-3 ,20-dione ace ta te
17α, 21 -d ihydroxy-4-pregnene-3,20-dione
l l / 3 , 17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
1 ,3 ,5 (10) -es t ra t r i ene-3 ,17 /3-diol (using spores)
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
21-hydroxy-4 -p regnene-3 ,20-dione
11/3,17a-dihydroxy-21-methyl-l , 4 - p r e g n a d i e n e - 3 , 2 0 , 2 1 -t r ione
4 -pregnene-3 ,20-d ione
REACTION
I4-OH
l | - O H
l | - O H
20-C=O -20/3-OH
2 0 - C = O -20/3-OH
16a-OH
d , l - 2 0 - C = O -d-20/3-OH + 1
2 0 - C = O -20/3-OH
2 0 - C = O -20/3-OH
16a-OH
16a-OH; 21-OAc - 2 1 - O H
2 0 - C = O -20/3-OH
2 0 - C = O -20/3-OH
17/3-OH -» 1 7 - C = 0
16a-OH
6/3-OH; 6/3,11a-diOH
11-oxygénation
2 0 - C = O -20/3-OH
6/3-OH; 6/3,11a-diOH
R E F .
F-234
F-234
F-234
K-470
K-470
V-1060
W-1094
K-470
K-470
L-491
L-491
K-470
K-470
S-835; V-1048
V-1060
S-929
H-328
A-6
S-929
nene-3,20-dione
TABLE I I I
Transformat ions by Genus·. STREPTOMYCES
637
SPECIES
f imicar ius
*
flaveolus *
1 f lavogriseus
1 fradiae
SOURCE
CBS
CZAS
CZAS
Shionogi (D-551)
Shionogi (H-4449)
Tokyo Univ. (4449)
C
CZAS (6 ,9 ; 6 ,10; 6 , 1 1 ; 6 ,15 ; 6 ,16; 6,17)
SUBSTRATE
4-pregnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17of, 21-d ihydroxy-4-pregnene-3,20-dione
11/3,17a, 21- t r i hydroxy-4 -p reg -nene-3 ,20-d ione
9a- f luoro- l l /3 ,17a , 21- t r ihydroxy-4-pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
11/3,17a, 21 - t r ihydroxy -4 - p r e g -nene -3 ,20-d ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
11/3,17a, 21-tr ihy d r o x y - 4 - p r e g -nene-3 ,20-d ione
3a, 7a, 12a-tr ihydroxy-5/3-cholanic acid
d, l -3 /3-hydroxy-5-pregnen-20-one
4 -p regnene-3 ,20-d ione
1 l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
11/3-hydroxy· 4 - p r e g n e n e - 3 , 2 0 -dione
REACTION
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH 1
Δ
Δ1; 2 0 - C = O -20/3-OH
1
Δ
Δ1; 2 0 - C = O -20/3-OH
20-C=O > 20/3-OH
2 0 - C = O -20/3-OH
3 a - O H - 3 - C = 0 ; 1 2 a - O H - 12-C = 0 ; Δ4
3 a - O H - 3 - C = 0 ; 12a-OH-+12-C = 0;17/3-CH(CH3) -CH2CH2COOH -17/3-CH(CH3)-COOH
d, l -3/3-OH—d-3-C=0+1-3 /3-OH; ά , 1 - Δ 5 -ά-Δ4+ 1-Δ5
6/3-OH; 6/3,11a-diOH
6/3-OH
6/3-OH
R E F .
P-745
P-745
P-745
P-745
P-745
V-1060
V-1060
K-470
K-470
K-470
K-470
K-470
K-470
H-357
S-784; S-785
W-1102
S-929; V-1061
V-1061
V-1061
TABLE I I I
Transformat ions by Genus: STREPTOMYCES
SPECIES
fradiae
fulvissimus
gelat icus (Actinomyces)
SOURCE
CZAS (6 ,9 ; 6 ,10; 6 , 1 1 ; 6 ,15 ; 6 ,16; 6,17)
SQ
WC (3535)
NRRL B-1453
Okayama Univ. Med. School(1164)
SUBSTRATE
17a-hydroxy-4 -p regnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
11/3,17a, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
4 -p r egnene -3 ,11 ,20 - t r i one
17a ,21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione
3/3-hydroxy-5-pregnen-20-one
3/3-hydroxy-5-pregnen-20-one
21-hydroxy-4 -p regnene-3 ,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
3a-hydroxy-5/3-cholanic acid
3α, 7α, 12a-tr ihydroxy-5/3-cholanic acid
REACTION
6/3-OH; 6/3,11a-diOH
6/3-OH; 6/3,11α-diOH
6/3-OH; 6/3,11a-diOH
6/3-OH
6/3-OH
6/3-OH
Δ 5 - Δ 4 ; 3/3-OH-* 3 - C = 0
Δ 5 ^ Δ 4 ; 3/3-OH-3 - C = 0
6/3-OH
11/3-OH
11/3-OH
11/3-OH; 1 1 - C = 0 (via 11/3-OH)
l | - O H
17/3-CH(CH3)-CH2CH2COOH-17/3-COOH; 3/3-O H - 3 - C = 0 ; Δ5—Δ4; Χ-ΟΗ
3a-OH-»3-C=0; 12a-OH—12-C = 0 ; A4;17/3-CH (CH3)- CH2 -CH2-COOH—17/3-CH (CH3)-COOH
1 2 a - O H - 1 2 - C = 0;17/3-CH(CH3) -CH2-CH2-COOH -17/3-CH(CH3)-COOH
3a-OH— 3 - C = 0 ; 7 α - Ο Η - Δ β ; 1 2 α -OH - 1 2 - C = 0 ; Δ4
R E F .
V-1061
V-1061
V-1061
V-1061
V-1061
V-1061
P-710
P-712
H-328
C-134
C-112; C-134; C-135; H-328
C-134; C-135; H-328
F-234
H-364
H-354; H-355; H-356; H-360; S-785
H-359
H-359; H-361
638
TABLE I I I
T ransformat ions by Genus: STREPTOMYCES
639
SPECIES
gelat icus (Actinomyces)
globisporus
SOURCE
Okayama Univ. Med. School(1164)
Shionogi (1164)
IPB
SUBSTRATE
3a, 7ö, 12o-trihydroxy-5]3-cholanic acid
3α, 7α, 12a-tr ihydroxy-5/3-cholanic acid (sole carbon source)
3 ,7 ,12 - t r ike to -5ß-cho lan ic acid
17a ,21-d ihydroxy-4-pregnene-3,20-dione
11/3, 17a, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
5-androstene-3/3,17a-diol
5-androstene-3j3,17/3-diol
3/3-hydr oxy - 5 -andr osten -17 -one (influence of s t e ro id on microbia l resp i ra t ion)
3/3-hydroxy-5-androsten-17-one ace ta te
REACTION
7α-ΟΗ-*Δ6;3α-ΟΗ->3-0=Ο;Δ 4 ; 17ß-CH(CH3)-(CH 2)2-COOH-17/3-CH(CH3)-COOH
3a-OH—3-C = 0
12a-OH-> 1 2 - C = 0
3 a - O H - 3 - C = 0 ; 12a-OH-»12-
c=o 3a-OH—3-C=0; 1 2 Λ - Ο Η - > 1 2 -C = 0 : 7 a - O H - > Δβ; Δ'4
util ization
7-C=0->7a-OH: Δ4
7-C = 0-*7a-OH;
-(CH2)2-COOH-> 17/3-CH(CH3)-COOH
2 0 - C = O -20)3-ΟΗ
2 0 - C = O -20/3-OH
Δ5—Δ ; 3/3-OH— 3 - C = 0
Δ5—Δ4;3β-ΟΗ— 3 - C = 0
Δ5—Δ ;3/3-OH— 3-C=0 ;17ß-OH ->17-C = 0
Δ —Δ ; 3/3-OH - 3 - C = 0
Δ ->Δ ; 3/3-OAc - 3 - C = 0
5 4
Δ —Δ ;3/3-OAc - 3 - C = 0 ; 1 7 -C=0-*17/3-OH
R E F .
H-359
H-366
H-366
H-366
H-366
S-784
H-3 63
H-363
K-470
K-470
H-337
H-337
H-337
C-106; C-107
H-335
H-335
Δ ;17i3-CH(CH3) 4
TABLE I I I
Transformations by Genus: STREPTOMYCES
SPECIES
globosus * (Actinomyces)
g r i seocarneus
gr i seo lus
g r i seus (var. casteneous) (var. cinnibarinus) (var. violaceus) (WC)
SOURCE
CZAA
ATCC-12628
CZAS
AMCY (LED-AD-1431)
AMCY (LED)
ATCC-13968
SUBSTRATE
4-pregnene-3 ,20-d ione
l l / 3 , 17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
9a - f luo ro - l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
11/3, 16α, 17α, 21 - te t rahydroxy-4-pregnene-3 ,20-d ione
9a- f luoro- l l /3 ,16α ,17α ,21- te tΓa-hydroxy-4 -p regnene -3 ,20 -dione
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
9a- f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
11/3,17a, 21- t r ihydr oxy - 1 , 4 -pregnadiene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
11/3,17a, 21 - t r ihydroxy-4 - p r e g -nene -3 ,20-dione
9a- f luoro- l l /3 ,17a , 21- t r ihydroxy-4-pregnene-3 ,20-d ione
11/3,17a, 21- t r ihydr o x y - 1 , 4 -pregnadiene-3 ,20-d ione
11/3,16a, 17a ,21- te t rahydroxy-4-pregnene-3 ,20-d ione 16 ,17 -acetonide
9a- f luoro- l l /3 ,16a , 17a, 2 1 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione 16, 17- acetonide
REACTION
16a-OH
I4-OH
1ξ-ΟΗ
1ξ-ΟΗ
1ξ-ΟΗ
6/3-OH
6/3,1 la-diOH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
2/3-OH
2/3-OH
R E F .
V-1060
F-234
F-234
F-234
F-234
S-929
S-929
P-745
P-745
P-745
P-745
P-745
P-745
P-745
P-745
P-745
P-745
P-745
F-235; F-236
F-235; F-236
640
TABLE I I I
Trans format ions by Genus: STREPTOMYCES
641
SPECIES SOURCE SUBSTRATE REACTION REF.
griseus ATCC-13968 6a, 9a-difluoro-ll/3,16a, 17a, 21 -tetrahydroxy-4-pregnene-3,20-dione 16,17-acetonide
9a:fluoro-ll/3,16a,17a,21-tetra-hydroxy -1,4-pr egnadiene-3,20-dione 16,17-acetonide
5a-androstane-3,17-dione
4-androstene-3,17-dione
5a-pregnane-3,20-dione
21-hydroxy-5a-pregnane-3,20-dione
17a, 21-dihy droxy-5a-pregnane-3,20-dione
4-pregnene-3,20-dione
16a-hydroxy-4-pregnene-3,20-dione
21-hydroxy-4-pregnene-3,20-dione
11/3,21-dihydroxy-4-pr egnene -3,20-dione
17a, 21-dihydroxy-4-pregnene-3,20-dione
11/3,17a, 21-trihydr oxy-4-pr eg-nene-3,20-dione
17a, 21 -dihydroxy -4-pregnene -3,11,20-trione
2/3-OH
2-OH
3-C=0—3/3-OH
Δ4-5α-Η
Δ4^5α-Η; 3-C=0-3/3-OH
3-C=0-3/3-OH
3-C=O-»30-OH
3-C=0—3/3-OH
Δ4^5α-Η
Δ -5a -H; 3-C=0-3/3-OH
Δ4—5α-Η; 3-C=0-3/3-OH
Δ4-5α-Η
Δ - 5 α -H; 3-C=0-3/3-OH
Δ4-5α-Η; 3-C=0-*3|3-OH
Δ4-5α-Η
Δ -5α-Η; 3-C=0-3ß-OH
3-C=O-3/3-0H; Δ4—5α-Η
3-C = 0—3/3-OH; Δ4-5α-Η
F-235; F-236
F-235: F-236
V-1059: W-1097
V-1059; W-1097
V-1059; W-1097
V-1059; W-1097
V-1059: W-1097
V-1059; W-1097
V-1059; W-1097
V-1059: W-1097
V-1059; W-1097
V-1051; V-1059; W-1097
V-1059: W-1097
V-1059; W-1097
V-1059; W-1097
V-1059; W-1097
W-1097
W-1097
c
642
TABLE I I I
Transformat ions by Genus: STREPTOMYCES
SPECIES
gr i seus *
halstedii
SOURCE
CZAS
NG
SCH (FC-103)
Shionogi
SQ
WC (No. 4; 3478)
ATCC-13499
SUBSTRATE
4-pregnene-3 ,20-d ione
1 ,3 ,5 (10 ) -e s t r a t r i ene -3 ,17a -d io l
l , 3 ,5 (10) -es t ra t r i ene-3 ,17 j3 -d io l
3 - h y d r o x y - l , 3 , 5 ( 1 0 ) - e s t r a t r i e n -17-one
5-cholesten-3/3-ol (sole carbon source)
24 /3-methyl -5 ,7 ,22-choles ta t r ien-3j3-ol (sole carbon source)
11/3,17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3 ,11 ,20 - t r ione
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - l , 4 -pr e gnadiene - 3 , 2 0 - dione
1 la, 21 -dihydroxy - 1 , 4 -pregna -diene - 3 , 1 1 , 2 0 - t r ione
17a, 21-dihydroxy-4-pregnene -3,20-dione
11/3; 17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
3/3-hydroxy-5-pregnen-20-one
3/3-hydroxy-5-pregnen-20-one
l ,3 ,5 (10) -es t r a t r i ene -3 ,17 /3 -d io i
3 - h y d r o x y - l , 3 , 5 (10) -es t ra t r ien-17-one
17a, 21-dihydroxy-4-pregnene-3,20-dione
9a-fluor o -11 j3,17a, 21- t r ihydroxy-4-pregnene-3 ,20-d ione 2 1 -aceta te
9a- f luoro- l l /3 ,17a , 21 - tr ihydroxy -4-pregnene-3 ,20-d ione 2 1 -propionate
REACTION
16a-OH
16a-OH
16a-OH
16a-OH
-
—
2 0 - C = O -20/3-OH
2 0 - C = O -20/3-OH
20-C=O-> 20/3-OH
2 0 - C = O - * 20/3-OH
2 0 - C = O -20/3-OH
2 0 - C = O -20/3-OH
Δ 5 -Δ 4 ;3 /3-ΟΗ - 3 - C = 0
Δ —Δ*;3/3-ΟΗ - 3 - C = 0
16a-OH
16a-OH;17/3-OH - 1 7 - C = 0
16a-OH
16a-OH;17-C = 0—17/3-OH
16a-OH
16a-OH;21-OAc - 2 1 - O H
16a-OH; 2 1 -OPr—21-OH
R E F .
V-1060
S-935
S-935
S-935
S-793c
S-793c
C-110
C-110
C-110
C-110
K-470
K-470
P-710
P-712
K-448
K-448
K-448
K-448
K-447
K-447
K-447
TABLE I I I
T ransformat ions by Genus: STREPTOMYCES
643
SPECIES
halstedii
1 hydrogenans
SOURCE
ces
IAM (3199)
NRRL B-2138
Hoechst (FAM)
(FHP-678)
SUBSTRATE
4-pregnene-3 ,20-d ione
21-hydroxy-4 -p regnene-3 ,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
l l / 3 , 17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
9 a - f l u o r o - l l ß , 1 7 a , 2 1 - t r i h y d r o x y -4-pregnene-3 ,20-d ione
9 a - f l u o r o - l l j 3 , 1 6 a , 1 7 a , 2 1 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione
3α, 7α, 12a-tr ihydroxy-5j3-cholanic acid (sole carbon source)
s eve ra l bile ac ids
l , 3 ,5 (10) -es t r a t r i ene -3 ,17 /3 -d io l
3 - h y d r o x y - l , 3 , 5 ( 1 0 ) - e s t r a t r i e n -17-one
9a - f luoro- l l j3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione 2 1 -aceta te
4 -pregnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione (induction of 20ß-hydroxy-dehydrogenase , Ref. N-656 -isolation and specificity , Ref. N-657 - purification and crys ta l l iza t ion , Ref. H-408; H-409; H-410; S-802; S-803)
l l a , 1 7 a , 2 1 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
REACTION
I4-OH
1ξ-ΟΗ
1ξ-ΟΗ
1ξ-ΟΗ
I f -OH
I l - O H
utilization
utilization
16a-OH
16a-OH;17/3-OH - 1 7 - C = 0
16a-OH
16a-OH; 17-C = 0 ->17β-ΟΗ
16a-OH;21-OAc - 2 1 - O H
-
2 0 - C = O -20/3-OH
2 0 - C = O -20/3-OH
REF.
F-234
F-234
F-234
F-234
F-234
F-234
H-357; S-784
S-785
K-448
K-448
K-448
K-448
K-447
L-522
L-522
H-408; L-522; N-656
H-408; L-522
644
TABLE I I I
Transformat ions by Genus: STREPTOMYCES
SPECIES
hydrogenans
1 hygroscopicus
lavendulae
SOURCE
Hoechst (F AM)
(FHP-678)
AMCY
AMCY (LED)
ATCC-8664
SQ (SC-1620)
AY
SUBSTRATE
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione
l l j 3 , 1 7 a , 2 1 - t r i h y d r o x y - l , 4 -pregnadiene -3 ,20-dione
17a, 21-d ihydroxy-1 ,4 -p regna-d i ene -3 ,11 ,20 - t r i one
l l / 3 , 17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
9a- f luoro- l l j3 , 17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
l l / 3 , 16a ,17a ,21 - t e t r ahyd roxy -4 -pregnene-3 ,20-d ione
9 a - f l u o r o - l l ß , 1 6 a , 1 7 a , 2 1 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione
11/3,17a, 21- t r ihydroxy-6a-methyl -1 ,4 -p regnad iene -3 ,20-d ione
11/3,17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
9a- f luoro- l l /3 ,17a , 21- t r ihydroxy-4-pregnene-3 ,20-d ione
19-nor -4 -p regnene-3 ,20-d ione
4-pregnene-3 ,20-d ione (adaptive enzyme; effect of antibiotics)
4 -pregnene-3 ,20-d ione
5-cholesten-3/3-ol
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
REACTION
20-C=O-+ 20/3-OH
2 0 - C = O -20/3-OH
2 0 - C = O -20/3-OH
2 0 - C = O ^ 20/3-OH
14-OH
1ξ-ΟΗ
1ξ-ΟΗ
1ξ-ΟΗ
1ξ-ΟΗ
I l - O H
I l -OH
1 Δ ; enol.
17/3-Ac — 1 7 - C = 0
Δ1; enol. 17/3-Ac-17/3-OH
17/3-Ac—17a- x o x a - 1 7 - C = 0 ^ ; enol.
Δ1; 17/3-Ac -1 7 - C = 0
1 Δ
Δ —Δ ; 3/3-OH - 3 - C = 0
1 Δ
2 0 - C = O -20/3-OH 1
R E F .
H-408; L-522; S-801
L-522
H-408; L-522
L-522
F-234
F-234
F-234
F-234
F-234
F-234
F-234
G-317
G-317
G-317
G-317
P-719
T-1005
T-1005
S-835; V-1048
S-835
TABLE I I I
Transformat ions by Genus: STREPTOMYCES
645
SPECIES
lavendulae
SOURCE
C
CZAS
NG
Shionogi (O-20-60)
(Waksman s t ra in)
WC (3440-14)
SUBSTRATE
d, 1-17α, 21 -dihydroxy-4 - p r e g -nene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
5-cholesten-3/3-01
24/3-methyl -5 ,7 ,22-choles ta t r ien-3/3-01
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
11/3 ,17û,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
l l / 3 ,17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
17/3 -hydr oxy -1 ,4 -andr ostadien -3-one
4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione 20-cycloethyleneketal
16a -hydroxy-4 -p regnene-3 ,20-dione
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
REACTION
d , l - 2 0 - C = O ^ d-20/3-OH + 1
16a-OH
-
Δ1; 2 0 - C = O ^ 20/3-OH
Δ1; 20-C = O -20/3-OH
20-C = O -20/3-OH
2 0 - C = O -20/3-OH
17/3-OH -1 7 - C = 0
17/3-Ac-17-C
17/3-Ac-17/3-OH; Δ1
ΔΧ;Πβ-Αο -> 17-C = 0
1
Δ ;17/3-Ac — 17/3-OH
20-C = O -20/3-OH
1
Δ
17/3-Ac-*17/3-OH
Δ1; 2 0 - C = O -20/3-OH
2 0 - C = O -20/3-OH
1
Δ
REF.
W-1094
V-1060
S-793c
S-793c
K-470
K-470
K-470
K-470
P-733
F-251
F-251
F - 2 7 1 ; F-284; P -733
F - 2 7 1 ; F-284; P-733
F - 2 7 1 ; F-284
F-251
F - 2 7 1 ; F-288
F - 2 7 1 ; F -273 ; F-288
F - 2 7 1 ; F -273 ; F-288
F-272
646
TABLE I I I
Transformat ions by Genus: STREPTOMYCES
SPECIES
lipmanii
*
mediocidicus
*
*
*
*
*
microflavus
1 * I n i t rosporeus
SOURCE
ATCC-3331
CZAS
ATCC-13278
ATCC-13279
ATCC-3332
CZAS
AMCY
SUBSTRATE
4-pregnene-3 ,20-d ione
21-hydroxy-4-p regnene-3 ,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
11/3,17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
9a - f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
l ,3 ,5 (10) -es t ra t r i ene-3 ,17 j3 -d io l
3 - h y d r o x y - l , 3 , 5 ( 1 0 ) - e s t r a t r i e n -17-one
4-pregnene-3 ,20-d ione
9a- f luoro- l l j3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
9a -fluor o -17a, 21 -dihydroxy - 4 -pr egnene - 3 , 1 1 , 2 0 - t r ione
l , 3 , 5 (10 ) - e s t r a t r i ene -3 ,17 /3 -diol
17/3-hydroxy-4-androsten-3-one
l l / 3 ,17a ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
9a- f luoro- l l /3 , 17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
21-hydroxy-4-p regnene-3 ,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
9a - f luoro - l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
11/3,17a, 21- t r ihydroxy-6a-methy l -1 ,4-pregnadiene-3 ,20-dione
REACTION
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH;17j3-OH - 1 7 - C = 0
16a-OH
16a-OH; 17-C = 0 ^17/3-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
1ξ-ΟΗ
1ξ-ΟΗ
1|-ΟΗ
1ξ-ΟΗ
R E F .
P-745
P-745
P-745
P-745
P-745
V-1060
K-448; S-788
K-448
K-448
K-448
S-788
S-788
S-788
S-788
S-788
P-745
P-745
V-1060
F-234
F-234
F-234
F-234
TABLE I I I
Transformat ions by Genus: STREPTOMYCES
647
SPECIES
n i t rosporeus
olivaceus *
olivochromogenus
parvus *
purpureochromogenus
SOURCE
IAM (O-20)
CZAS
WC (3688)
ATCC-3336
ATCC-13025 MCC (MA-320)
CZAS
NRRL
ATCC-3133
SUBSTRATE
3a-hydroxy-5/3-cholanic acid (sole carbon source)
3Q, 7o, 12a- t r ihydroxy-5ß-cholanic acid (sole carbon source)
3α, la, 12a-trihydroxy-5/3-cholanic acid conjugated with glycine-glycocholic acid (sole carbon source)
3a, la, 12a-tr ihydroxy-5/3-cholanic acid conjugated with taur ine -taurocholic acid (sole carbon source)
3 ,7 ,12- t r iketo-5/3-cholanic acid (sole carbon source)
4 -p regnene-3 ,20-d ione
17/3-hydr oxy -4 -androsten -3 -one
4 -andros tene -3 ,17-d ione
4 -p regnene-3 ,20-d ione
21 -hydroxy-4 -p regnene -3 ,20 -dione
l l / 3 , 17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3 ,11 ,20 - t r ione
9a - f luoro - l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione 2 1 -aceta te
4 -p regnene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
4 -p regnene-3 ,20-d ione
REACTION
utilization
utilization
utilization
utilization
utilization
16a-OH
16a-OH
16«-OH
16a-OH
16a-OH
1
Δ
1
Δ
Ιξ-ΟΗ-21-OAc —21 -OH
20-C = O->20/3-OH;21-OAc -21-OH
6/3-OH;21-OAc ->21-OH
21-OAc-21-OH
16a-OH
-
-
-
16a-OH
R E F .
S-785
H-357; S-784
S-785
S-785
S-785
S-929; V-1060
F-265
F-265; F-267
F-265; F-267
F-265; F-267
C-125
C-125
M-569; S-941
M-569; S-941 '
M-569; S-941
S-941
V-1060
M-587
M-587
M-587
P-745
648
TABLE I I I
Transformat ions by Genus: STREPTOMYCES
SPECIES
purpureochromogenus
*
r imosus
1 roseochromogenus
SOURCE
ATCC-3133
CZAS
AY
CZAS
LED (T-1686B)
NG
NRRL-2234
SQ
AMCY (LED)
SUBSTRATE
21-hydroxy-4 -p regnene-3 ,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
l l / 3 ,17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
9a - f luoro - l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
4 -p regnene -3 , 20-dione
l ,3 ,5 (10) -es t ra t r i ene -3 ,17 i3 -d io l (with spores)
4 -pregnene-3 ,20-d ione
9a - f luoro- l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
l , 3 , 5 ( 1 0 ) - e s t r a t r i e n e - 3 , 1 7 a - d i o l
l ,3 ,5 (10) -es t ra t r i ene-3 ,17)3-d io l
3 - h y d r o x y - l , 3 , 5 ( 1 0 ) - e s t r a t r i e n -17-one
3/3-hydroxy-5-pregnen-20-one
4-pr e gnene - 3,2 0 - dione
5-cholesten-3/3-ol
3/3-hydroxy-5-pregnen-20-one
9a - f luoro - l l /3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
21-(n-ace ty lamino)-9a-f luoro-l l ß , 17a-dihydroxy-4-pregnene-3,20-dione
21-amino-9a- f luoro- l l /3 ,17a-d ihydroxy-4-p regnene-3 ,20-dione hydrochloride
9a - f luoro - l l /3 ,17a ,21- t r ihydroxy-1,4 -pr egnadiene -3 ,20-d ione
21 - (n -acety lamino) -9a -fluor o -11/3 ,17a-d ihydroxy- l ,4-pregna-d iene-3 ,20-d ione
REACTION
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
1 7 / 3 - O H -1 7 - C = 0
6/3-OH
6/3, l la-diOH
6/3-OH
16a-OH
16a-OH
16a-OH
Δ5—Δ ; 3/3-OH - 3 - C = 0
1
Δ
Δ 5 ^ Δ 4 ; 3/3-OH - 3 - C = 0
Δ 5 - Δ \ · 3/3-OH - 3 - C = 0
21-OH-»21-AcNH
2β-ΟΗ (tentative)
2 1 - N H 2 - 2 1 -AcNH
21-OH-^21-AcNH
—
R E F .
P-745
P-745
F-234; P-745
P-745
V-1060
S-835; V-1048
S-929
S-929
S-909
S-935
S-935
S-935
P-712
T-1005
T-1005
P-710
S-911
S-911
S-911
S-911
S-911
TABLE I I I
Transformations by Genus: STREPTOMYCES
649
SPECIES SOURCE SUBSTRATE REACTION REF.
roseochromogenus AMCY (LED-409)
ATCC-3347
9a - f luoro-11ß-hydroxy-4-androstene-3,17-dione
4-estren-3-one
16a-hydroxy-4-estren-3-one
16/3-hydroxy-4-estren-3-one
4-estren-3,16-dione
3/3-bromo-19-nor-5-pregnen-20-one
3/3-chloro-19-nor-5-pregnen-20-one
3/3-fluoro-19-nor-5-pregnen-20-one
3/3-hydroxy-19-nor-5-pregnen-20-one
11/3,21 -dihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
9a -fluoro -1 Iß, 21 -dihydroxy -4-pregnene-3,20-dione
lla,17a,21-trihydroxy-4-preg-nene-3,20-dione
11/3,17a,21-trihydroxy-4-preg-nene-3,20-dione
16a-OH
16a-OH
16/3-OH
16-C=0(via either 16a or 16/3 -OH)
16a-OH^16/3-OH (vial6-C=0)
16a-OH^16-c=o
16/3-OH — 16-C=0
1 6 - C = 0 -16/3-OH
16a-OH
B-62
S-793a
S-793a
S-793a
S-793a
S-793a
S-793a
S-793a
Z-1128
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH; 16a, 17a-diOH-17/3-(20-C=O-21-OH) —>D-homo-16a, 17aa-diOH-17a/3-CH 2 OH-17-C=0
16a-OH
Z-1128
Z-1128
Z-1128·, Z-1129
H-399
H-399
H-403
G-295; G-297
G-297
G-295; G-297; H-399
650
TABLE 111
Transformat ions by Genus: STREPTOMYCES
SPECIES
roseochromogenus
SOURCE
ATCC-3347
SUBSTRATE
l l / 3 , 17a ,21 - t r i hyd roxy -4 -p reg -nene-3 ,20-d ione
9a -ch lo ro - l l j 3 ,17a ,21 - t r ihydroxy-4-pregnene-3 ,20-d ione
6a - cyano -9a - f l uo ro - l l / 3 , 17a ,21 -t r i hyd roxy -4 -p regnene -3 ,20 -dione
9a- f luoro- l l j3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
(s t rain var ia t ion - Ref. G-298)
(Ref. G-297, p r e s e n c e of
a non-biologie i somer ization of th is subs t ra te to D-homo compound)
9a -ch lo ro -2 /3 , l l | 3 ,17a ,21 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione
9a -ch lo ro - l l / 3 ,16a , H a ^ l - t e t r a -h y d r o x y ^ - p r e g n e n e - S , 20-dione
9a-fluoro-2/3,11/3,17a, 2 1 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione (see note Ref. G-297)
9 a - f l u o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione
6a - cyano -17a, 21-dihydr oxy-4-p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - l , 4 -pregnadiene-3 ,20-d ione (see note Ref. G-297)
6a - f luoro- l l /3 ,17a ,21- t r ihydroxy-1,4-pr egnadiene - 3 ,20-dione
REACTION
16a-OH; 16a, 17a-diOH-17ß-(20-C=O-21-OH) —>D-homo -16a -17aa-diOH-17aß-CH 2 OH-17-C=0
2/3-0H
16a-OH
2ß-OH
2/3-OH
16a-OH
16a-OH;17a-OH-17/3-(20-C=O-21-OH)-*17aa-OH-17aß-CH2OH-1 7 - C = 0
2/3,16a-diOH
16a-OH
2/3-OH
16a-OH
2/3-OH
16a-OH
16a-OH
16a-OH
R E F .
G-297
S-913
3 -74
G-298; S-913
S-912
G-295; G-297; L-505; S-913
G-295; G-297; G-298; L-505; S-910; S-912; S-913
G-298; S-912; S-913
S-913
S-913
S-912; G-297
S-913
B-74
G-295; G-297
H-399
ferrie or ferrous ion leads to
TABLE I I I
T ransformat ions by Genus: STREPTOMYCES
651
SPECIES SOURCE SUBSTRATE REACTION R E F .
roseochromogenus
(Krainsky)
ATCC-3347
AY
CZAS
Shionogi ^0-36)
SQ
WC(3689)
9a - f luoro- l l /3 ,17a ,21- t r ihydroxy 1 ,4-pregnadiene-3 ,20-d ione (Δ1 of subs t ra te blocks 2/3-OH)
6 a - c y a n o - 1 7 a , 2 1 - d i h y d r o x y - l , 4 -pr egnadiene - 3 , 1 1 , 2 0 - t r ione
17a, 21-dihydroxy-4-pregnene -3,20-dione (with conidia)
3/3-hydroxy -19 -nor_-5a -pregnan-20-one
3/3-hydroxy-5a-pregnan-20-one aceta te
11/3,21 -dihydroxy -4 -pr egnene -3,20-dione 18-oic acid (18^11)- lac tone
4-pregnene ^3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
11/3,17a, 21 - t r ihydroxy -4 - p r e g -nene -3 ,20-d ione
D - homo -17a - oxa - 1 , 4 - andr o s t a -d iene-3 ,17-d ione
A-nor -3 -p regnene -2 ,20 -d ione
4 -andros tene -3 ,17-d ione
17/3-hydroxy-4-androsten-3-one
21 -hydroxy-4 -p regnene -3 ,20 -dione
17/3-hydroxy-4-androsten-3-one
4 -andros tene -3 ,17-d ione
A - n o r - D - h o m o - 1 7 a - o x a - 3 -andros tene -2 ,17-d ione
D - homo-17a -oxa -1 ,4 -and r osta -d iene-3 ,17-d ione
9a - f luoro- l l /3 -hydroxy-4-andro-s t ene -3 ,17-d ione
16a-OH
16a-OH
16a-OH;17a-OH -17/3-(20-C=O-2 1 - O H ) - 1 7 a a -OH-17a/3-CH2OH - 1 7 - C = 0
16a-OH
16a-OH
3/3-OAc->3/3-OH; 16a-OH
16a-OH
16a-OH
Δ1; 20-C = O 20/3 -OH
Δ1; 20-C=O 20/3-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
G-298
ß - 7 4
G-297
S-835; V-1048
W-1093
W-1092
vV-1091
V-1060
K-470
K-470
P-706
L-502
F-288
F-288
F-288
F-265
F-265 ; F-267
L-503
T-1000
T-1008
c
652
TABLE I I I
Transformat ions by Genus: STREPTOMYCES
SPECIES
roseochromogenus
SOURCE
WC (3689)
SUBSTRATE
9 a - c h l o r o - 4 - a n d r o s t e n e - 3 , 11 ,17-t r ione
9ö - f luo ro -4 -and ros t ene -3 ,11 ,17 -t r ione
A-nor -3 -p regnene -2 ,20 -d ione
4 -pregnene-3 ,20-d ione
21-hydroxy-4 -p regnene-3 ,20-dione
12a-bromo-11/3-hydroxy-4-pregnene-3 ,20-d ione
12a-ch loro- l l /3 -hydroxy-4-pregnene-3 ,20-d ione
nene-3 ,20-d ione
12a-fluoro-11/3-hydroxy -4 - p r e g -nene -3 ,20-dione
12ö-f luor0-21-hydroxy-4-preg-nene-3 ,20-d ione
11/3,17a-dihydroxy-4-pregnene -3,20-dione
1 l/3-hydroxy-6a- methyl - 4 -pregnene-3 ,20-d ione
11/3-hydroxy - 12a -me thy l -4 -p reg -nene-3 ,20-d ione
21 -hydroxy-11/3,12/3-oxido-4-pregnene-3 ,20-d ione
6a- f luoro- l l /3 ,17a-d ihydroxy-4-pregnene-3 ,20-d ione
9a- f luoro- l l /3 , 17α-dihydroxy -3 ,20-d ike to -4-pregnene-21-a l
11/3,17a-dihydroxy-6a-methyl-4-pregnene-3 ,20-d ione
9a-f luoro-11/3,17a-dihydroxy-6a-methy l -4 -pregnene-3 ,20-d ione
21-f luoro- l l /3 ,17a-d ihydroxy-6a-me thy l -4 -p regnene -3 ,20 -d ione
REACTION
Ιβα-ΟΗ
16α-OH
16α-ΟΗ
16α-OH
16α-OH
16α-OH
16α-OH
16α-OH
16α-OH
16α-OH
16α-OH
16α-OH
16α-ΟΗ
16α-OH
16α-OH
2 1 - C = 0 - > 21-OH
2 1 - C = 0 ^ 21-OH; 20-C = O —20/3-OH
16a-OH
16a-OH
16a-OH
R E F .
T-1008
T-1008
L-506
F-265; F-267
F-265; F-267
F-256
F-256
B-35
F-256; F-257
F-256
F-256
S-834
F-257
D-156; D-157
M-530
S-907
S-907
L-511
L-511
L-510
6o!-fluoro-ll/3-hydroxy-4-preg-
TABLE I I I
Transformat ions by Genus: STREPTOMYCES
653
SPECIES SOURCE SUBSTRATE REACTION R E F .
roseochromogenus WC (3689) 6a ,21 -d i f luo ro - l l / 3 ,17a -d i -hydroxy-4 -p regnene -3 ,20 -dione
6a- f luoro- l l j3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
9a- f luoro- l l j3 ,17a ,21- t r ihydroxy-4-p regnene-3 ,20-d ione (s t rain var ia t ion , Ref. G-298)
16a-OH
16a-OH
12a-f luoro- l l /3 ,17a,21- t r ihydroxy- | 4 -p regnene-3 ,20-d ione
6a - f luoro- l l j3 ,17a ,21- t r ihydroxy-9 a - m e t h y l - 4 - p r e g n e n e - 3 , 2 0 -dione
9a - f luo ro - l l / 3 ,17a ,21 - t r ihydroxy-12a -me thy l -4 -p regnene -3 ,20 -dione
6 a , 9 a - d i f l u o r o - l l / 3 , 1 7 a , 2 1 - t r i -hyd roxy-4 -p regnene -3 ,20 -dione
6 a , 1 2 a - d i f l u o r o - l l ß , 17α, 2 1 -t r i h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
9a, 21-dif luoro-l l /3,17a-dihydroxy- | 6 a - m e t h y l - 4 - p r e g n e n e - 3 , 2 0 -dione
6a, 9a, 2 1 - t r i f l u o r o - l l ß , 17a-d i -hydroxy-4 -p regnene -3 ,20 -dione
1 2 a - b r o m o - 4 - p r e g n e n e - 3 , 1 1 , 2 0 -t r ione
1 2 a - c h l o r o - 4 - p r e g n e n e - 3 , 1 1 , 2 0 -t r ione
6 a - f l u o r o - 4 - p r e g n e n e - 3 , 1 1 , 2 0 -t r ione
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
M-532
M-533;
2/3-OH
16a-OH
2/3,16a-diOH
2 0 - C = O -20/3-OH
16a-OH; 20-C=O-20/3-OH
16a-OH
16a-OH
M-534; M-586
G-298; S-913
G-298; S-913; T-1002
G-298
S-907
S-907
F-256; F-257
F-260
F-260
M-533; M-586
F-261
L-510
M-532
F-256
F-257
B-35
654
TABLE I I I
Transformat ions by Genus: STREPTOMYCES
SPECIES
roseochromogenus
SOURCE
WC (3689)
SUBSTRATE
12a - f luo ro -4 -p regnene -3 ,11 ,20 -t r ione
6 a - m e t h y i - 4 - p r e g n e n e - 3 , 1 1 , 2 0 -t r ione
12a- f luor0-21-hydroxy-4-preg-n e n e - 3 , l l , 2 0 - t r i o n e
12a -chloro -1 la, 21 -dihydroxy -4 -p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
12a-f luoro-17a ,21-dihydroxy-4-p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
12a -ch lo ro -6a - f luo ro -17a ,21 -d ihydroxy-4 -p regnene -3 ,11 , 20- t r ione
21-hydroxy- l l /3 ,12/3-oxido- l ,4-pregnadiene-3 ,20-d ione
11/3,1 la -dihydr oxy- 6a- methyl -l , 4 -p regnad iene -3 ,20 -d ione
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - l , 4 -pr egnadiene -3 ,20-dione
6a- f luoro- l l /3 , 17a ,21- t r ihydroxy-1,4 -pr egnadiene -3 ,20-dione
9a - f luo ro - l l /3 ,17a ,21- t r ihydroxy-1,4-pr egnadiene-3 ,20-dione (Δ1 of subs t ra te blocks 2/3-OH -Ref. G-298)
12α-fluoro-11/3,17a,21-tr ihydroxy - 1 , 4 - p r egnadiene-3 ,20-dione
9o-f luoro-l l j3 ,17α-dihydr oxy-6α-me thy 1-1,4-pr egnadiene - 3 , 20-dione
2 1 - f i u o r o - l l ß , 17α -dihydr oxy -6a -m e t h y l - l , 4 - p r e g n a d i e n e - 3 , 2 0 -dione
6a, 21-difluor o- l l /3 ,17a-dihydr oxy - l , 4 - p r e g n a d i e n e - 3 , 2 0 - d i o n e
l l /3 ,17a ,21- t r ihydroxy-6a-methy l - l , 4 - p r e g n a d i e n e - 3 , 2 0 - d i o n e
9a - f luoro- l l /3 ,17a ,21- t r ihydroxy-6 a - m e t h y l - l , 4 - p r e g n a d i e n e -3,20-dione
9a, 21-difluoro-11/3,17a-dihydr oxy -6a -me thy 1-1,4-pr egnadiene-3,20-dione
REACTION
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
16a-OH
REF.
F-256
S-834
F-256
F-256; F-257
F-256
F-261
D-157
L-511
F-257
M-531
G-298; T-1002
F-256; F-257
L-511
L-510
M-532
F-257
F-257
L-510
TABLE I I I
T ransformat ions by Genus: STREPTOMYCES
655
SPECIES
roseochromogenus
ruber
rubescens
SOURCE
WC (6389)
NRRL (B - 1268)
IAM (Z-52)
SUBSTRATE
6 a , 9 a , 2 1 - t r i f l u o r o - l l / 3 , 1 7 a -dihydroxy - 1 , 4 -pr egnadiene -3,20-dione
12a-f luoro-17a, 21 -dihydroxy- i , 4 -p regnad iene-3 ,11 ,2G- t r ione
4 -p regnene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
9 a - f l u o r o - l l ß , 17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
9 a - f l u o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione
9a- f luoro- l l /3 ,16a , 17a, 21 - t e t r a -hydroxy-1 ,4-pregnadiene -3,20-dione
3a-hydroxy-5/3-cholanic acid (sole carbon source)
3a, 7a, 12a- t r ihydroxy-5ß-choianic acid (sole carbon source)
3α, 7α, 12a-tr ihydroxy-5j3-cholanic acid conjugated with glycine-glycocholic acid (sole carbon source)
3a, 7a, 12a-tr ihydroxy-5/3-cholanic acid conjugated with taur ine -taurochol ic acid (sole carbon source)
3 ,7 ,12 - t r ike to -5ß -cho lan ic acid (sole carbon source)
REACTION
16a-OH
16a-OH
1ξ-ΟΗ
l | - O H
1ξ-ΟΗ
1ξ-ΟΗ
1ξ-ΟΗ
1ξ-ΟΗ
utilization
util ization
3a-OH-+3-C=0; 7α-ΟΗ->Δ6;12α-O H ^ 1 2 - C = 0 ; 5β-Η-*Δ4
3 a - O H - 3 - C = 0 ; Δ4-(5/3-Η)
3a-OH-*3-C=0; 12a-OH-+12-C=0 Δ4-(5/3-Η)
3a-OH->3-C=0; 7 α - Ο Η - Δ 6 ; Δ4-(5β-Η)
uti l ization
util ization
uti l ization
R E F .
M-532
F-256
F-234
F-234
F-234
F-234
F-234
F-234
S-785
H-357; S-784
H-365
H-365
H-365
H-362
S-785
S-785
S-785
656
TABLE I I I
Transformations by Genus: STREPTOMYCES
SPECIES
rubr i r e t i cu l i
rubrocyanodias ta t icus
r u t g e r s e n s i s
scabies
setonii
spec ies
(species l a te r ident-ified a s argenteolus)
SOURCE
AMCY (LED)
Shionogi
NRRL
IAM (3111)
SUBSTRATE
CZAS
AMCY (LED-AC-
209)
ATCC-11009
C (A-7747)
l l / 3 ,17a ,21 - t r i hyd roxy-4 -pregnene-3 ,20-d ione
9a- f luoro- l l /3 , 17α, 21 - tr ihydroxy -4 -pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
11/3,17a, 21 - t r ihydroxy-4 -p reg -nene-3 ,20-d ione
Sarsasapogenin
Diosgenin
4-dehydr otigogenone
3a-hydroxy-5/3-cholanic acid (sole carbon source)
3a, 7a, 12a - t r ihydr oxy - 5/3 -cholanic acid (sole carbon source - Ref. S-784)
3α, 7α, 12a-tr ihydroxy-5/3-cholanic acid conjugated with glycine-glycocholic acid (sole carbon source)
3a, 7a, 12a - tr ihydroxy -5/3-cholanic acid conjugated with taur ine- taurochol ic acid (sole carbon source)
3 ,7 ,12- t r ike to -5ß-cho lan ic acid (sole carbon source)
4 -p regnene-3 ,20-d ione
2 - f l uo ro -17a ,21 -d ihyd roxy - l , 4 -p regnad iene -3 ,11 ,20 - t r i one
3/3-hydroxy-5-pregnen-20-one
3/3-hydroxy-19-j ior-5a-pregnan-20-one
3/3-hydroxy-5a-pregnan-20-one
3/3-hydroxy-5/3-pregnan-20-one
9a-fluoro-3/3, l l /3-dihydroxy-5a-pregnan-20-one
REACTION
14-OH
I l - O H
2 0 - C = O ^ 20/3-OH
2 0 - C = O ^ 20ß-OH
utilization
util ization
util ization
utilization
util ization
16a-OH
REF.
3/3-OH->3-C=Oj Δ 5 - Δ 4
16a-OH
16a-OH
16a-OH
16a-OH
F-234
F-234
K-470
K-470
M-587
M-587
M-587
S-785
H-357; S-784
S-785
S-785
S-785
V-1060
A ^ H ( 2 a - F ) IH-402
F-267 P-710; P-712 P-716
W-1093
N-653: W-1092
W-1092
W-1092
TABLE I I I
Transformat ions by Genus: STREPTOMYCES
657
SPECIES
species
SOURCE
C (A-7747)
MCC (MA-449)
NG
QM-1086
S (8)
(27)
SUBSTRATE
3/3-hydroxy-5a-9(ll)-pregnen -20-one acetate
21-hydroxy-4-pregnene-3,20-dione
d, l-21-hydroxy-4-pregnene-3,20-dione
l lß , 21 -dihydroxy-4-pregnene-3,20-dione 18-oic acid (18^11) lactone
17a, 21 -dihydroxy -4 -pregnene -3,11,20-trione
5-cholesten-3/3-ol 14
5-cholesten-3/3-ol 4-C 14
5-cholesten-3/3-ol 26-C
17a, 21 -dihydroxy-4-pregnene-3,20-dione
ll/3,17a,21-trihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4-pregnene -3,11,20-trione
ll/3,17a,21-trihydroxy-l,4-pr e gnadiene -3,20- dione
17a, 21 -dihydroxy -1,4 -pregna-diene-3,11,20-trione
4-pregnene-3,20-dione
17a-hydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
4-pregnene-3,20-dione
17a-hydroxy-4-pregnene-3,20-dione
21-hydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
REACTION
16a-OH; 3/3-OAc ^3ß-OH
16a-OH
d,l^d-16a-OH + 1
16a-OH
Δ4-5β-Η; 3-C=0—3a-OH
utilization
utilization
utilization
20-C=O-» 20/3-OH
20-C=O-20/3-OH
20-C=O-20/3-OH
20-C=O-20/3-OH
20-C=O-* 20/3 -OH
16a-OH
-
—
16a-OH
-
-
REF.
W-1092
V-1054
W-1102
W-1091
B-41
D-145
D-145
D-145
C-110
C-110
C-110
C-110
C-110
S-847; S-849; S-859
S-859
S-859
S-847; S-859
S-849; S-859
S-849
S-849; S-859
658
TABLE I I I
Transformat ions by Genus: STREPTOMYCES
SPECIES
species (s t ra in 8 ,27 ,41 ,44 -Actinomyces)
SOURCE
S (41)
(44)
(72)
(103)
(161)
SCH (DS-81B,FC-6 - 5 3 S , F C - 7 -206)
(FC-B-222)
Shionogi (1-13)
SUBSTRATE
4-pregnene-3 ,20-d ione
17a-hydroxy-4-p regnene-3 ,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
1 l a -hydroxy-4 -p regnene -3 ,20 -dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
17ûi-hydroxy-4-pregnene-3,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihy dr oxy-4-pr egnene -3,20-dione
REACTION
6/3,1 la-diOH
-
16a-OH
-
-
16a-OH
6/3-OH
6/3,1 l a -diOH
-
6ß-OH
l l a - O H
6/3-OH
l l a - O H
16a-OH
2/3-OH
2 0 - C = O -20/3-OH
1
Δ
20-C = O -20/3 -OH
Δ1; 2 0 - C = O -20/3-OH
R E F .
S-859
S-859
S-859
S-847; S-859
S-859
S-859
S-847
S-847; S-854; S-859
S-847; S-854; S-859
S-859
S-847; S-849
S-847; S-849
S-847; S-849; S-854
S-847; S-854
S-847
H-383
C-110
K-470
K-470
K-470
TABLE I I I
T ransformat ions by Genus: STREPTOMYCES
659
SPECIES
spec ies
tanashiens is
tendae
thioluteus
SOURCE
Shionogi (1-13)
SQ (SC-1646, SC-3309, SC-3310, SC-3311)
SY (J-6-11)
uc
(BC-17 ,H-3 9 , K - 9 3 , W -4)
(H-39)
WC (3676)
WC (3808)
Shionogi
Shionogi (ETH-11313)
Shionogi (OKAMI)
SUBSTRATE
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
5-cholesten-3/3-01
17a, 21-dihydroxy-4-pregnene -3,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione (revision of s t ruc tu re a t 20 -see Ref. S-832)
17α, 21 -dihydroxy -4-pregnene -3,20-dione
4 -pregnene-3 ,20-d ione
17a, 21 -d ihydroxy-1 ,4 -p regna -d i e n e - 3 , 1 1 , 2 0 - t r i o n e
17a, 21 - dihydroxy -16a - methyl -1,4 -p r egnad i ene -3 ,11 ,20 -t r ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
l l / 3 , 17a ,21 - t r i hyd roxy -4 -pregnene-3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
11/3,17a, 21 - t r ihydroxy-4 - p r e g -nene -3 ,20-d ione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
11/3,17a, 21 - t r i h y d r o x y - 4 - p r e g -nene-3 ,20-d ione
REACTION
Δ1; 2 0 - C = O -20/3-OH
20-C=O-> 20/3-OH
1
Δ 1
Δ
Δ 5 -Δ 4 ;3 /3-ΟΗ - > 3 - C = 0
6/3-OH
11/3-OH
6/3,11/3-diOH
2 0 - C = O -20/3-OH
11-oxygénation
oxidation
15α-OH
Δ4-»5/3-Η
Δ 4 - 5 β - Η
Δ1; 20 -C=O-> 20/3-OH
Δ1; 2 0 - C = O -20/3-OH
2 0 - C = O -20/3-OH
2 0 - C = O -20/3-OH
2 0 - C = O - » 20/3-OH
2 0 - C = O ^ 20/3-OH
REF.
K-470
K-470
K-470
T-1005
T-1005
C-112
C-112
C-112
E-202
H-328
H-328
F-285; F-287
G-314
G-314
K-470
K-470
K-470
K-470
K-470
K-470
SPECIES
vinaceus *
v i r idans
vir idifaciens
v i r id is
*
vir idochromogenes (Actinomyces)
SOURCE
ATCC-11861
Shionogi
ATCC-11389
AY
CZAS
WC (3690)
CZAS
IPB
SUBSTRATE
4-pregnene-3 ,20-d ione
21-hydroxy-4 -p regnene-3 ,20-dione aceta te
17α, 21-d ihydroxy-4-pregnene-3,20-dione
11)3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
l l ß , 17a, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
9a - f luoro- l l j3 ,17a ,21- t r ihydroxy-4-pregnene-3 ,20-d ione
17a, 21 -dihydroxy-4,9(11) -p regna-d iene-3 ,20-d ione
17a, 21 -dihydroxy-4-pregnene -3,20-dione (with spores)
4 -p regnene-3 ,20-d ione
17/3-hydroxy-4-androsten-3-one
4 -andros tene-3 ,17-d ione
4 -pregnene-3 ,20-d ione
21-hydroxy-4 -p regnene-3 ,20-dione
4 -p regnene-3 ,20-d ione
5-androstene-3/3,17/3-diol
5-androstene-3/3,17a-diol
3ß-hydroxy-5-andros ten-17-one aceta te
REACTION
16α-OH
16a-OH;21-OAc - 2 1 - O H
20-C = O-> 20/3-OH
2 0 - C = O ^ 20j3-OH
1ξ-ΟΗ
1ξ-ΟΗ
1ξ-ΟΗ
14-OH
16α-OH
16α-OH
16α-OH
16α-ΟΗ
16α-OH
16α-OH
3/3-OH->3-C = 0 ; Δ 5 - Δ 4 ; 17)3-OH - 1 7 - C = 0
3)3-OH^3-C = 0 : Δ 5 - Δ 4
3 )3-OAc^3-C=0: Δ —»Δ
3/3-OAc—3-C=0; Δ 5 - Δ 4 ; 1 7 - 0 = 0 ^17)3-OH
R E F .
L-491
L-491
K-470
K-470
F-234
F-234
F-234
F-234
S-835; V-1048
V-1060
F-265
F-265 ; F-267
F-265 ; F-267
F -265 ; F-267
S-929
H-337
H-337
H-335
H-335
TABLE I I I
STREPTOMYCES T r a n s f o r m a t i o n s by Genus:
660
661
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: STREPTOMYCES STROPHARIA
STYSANUS SYNCEPHALASTRUM
(Basidio. - Agar ica les) (Imperf. - Moniliales) (Phyco. - Mucorales)
SPECIES
vi r idochromogenes
wil lmorei
STROPHARIA
cubensis
nordmanii
STYSANUS
1 médius
SYNCEPHALASTRUM
1 c incereum 1 (cinereum)
1 r acemosum
1 *
SOURCE
NRRL
NRRL B-1332
SY
AL (SS-74)
FRI
SSSR
IAM (6801)
SUBSTRATE
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
11/3,17a, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
9a -f luor o -1118,17a, 21 - t r ihy dr oxy -4 -p regnene-3 ,20-d ione
17a, 21 -dihydr oxy -4 -pr egnene -3,20-dione
4 -p regnene-3 ,20-d ione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
4 -p regnene-3 ,20-d ione (Ref. T-1025 c o r r e c t s con-figuration at 7 to 7/3 in Ref. A - 2 6 , 2 7 , 3 0 ; T-1020,1021) (species identified a s r a c e m o s u m in Ref. A-27)
REACTION
-
-
-
16a-OH
16a-OH
l l a - O H
oxidation -products not identified
6/3-OH; l l a - O H
l l a - O H
15/3-OH
6/3,1 la -d iOH •
6/3,15/3-diOH
7/3,15/3-diOH
7/3,14a, 15/3-tr iOH
Δ4-+5α-Η; 15/3-OH; 6 - C = 0 (via 6/3-OH)
R E F .
M-587
M-587
M-587
P-745
P-745
C-113
S-825
S-849
E-224
S-793
S-793
S-793
A-26; A-27; A-30; S-793; T-1020; T-1025
A-26; A-27; A-30; S-793; T-1021; T-1025
S-793
662
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: SYNCEPHALASTRUM SYNCEPHALIS (Phyco. - Mucorales)
TAPHRINA (Asco. - Taphrinales) THAMNIDIUM (Phyco. - Mucorales)
SPECIES
racemosum
spec ies
SYNCEPHALIS
nodosa
reflexa
TAPHRINA
diformans (deformans)
pruni
THAMNIDIUM
elegans
SOURCE
IAM (6801)
SSSR
NRRL
UC
UC
TNAES
TNAES
SQ
SSSR
SUBSTRATE
l l a - h y d r o x y - 4 - p r e g n e n e - 3 , 20-dione
6/3, l l a - d i h y d r o x y - 4 - p r e g n e n e -3,20-dione
7j3,15/3-dihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
11/3,1 la, 21 - t r ihydr oxy -4 - p r e g -nene-3 ,20-d ione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
plant saponins
not given
not given
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3 ,20-dione
4 ,9(11)-pregnadiene-3 ,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
REACTION
6/3-OH
-
14a-OH
l l a - O H
-
6/3-OH; l l a - O H ; 11/3-OH
-
oxidation
oxidation
—
—
6/3,12a-diOH
l l a - O H ; 11/3-OH; 1 1 - C = 0 (via 11/3-OH)
REF.
A-27; T-1020
A-27
T-1021
A-27; T-1020
A-27
E-224
K-478
M-601; M-636
M-601; M-636
S-849
S-849
F-277; F-279
E-224
663
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: THIEL A VIA
THYROSPORA TIEGHEMELLA
TILLETIOPSIS
(Asco. - Eurot ia les) (Imperf. - Moniliales) (Phyco. - Mucorales) (Imperf. - Moniliales)
SPECIES
THIELAVIA
basicola
t e r r i co l a
THYROSPORA
as t r aga l i
TIEGHEMELLA 1 (synonym - Absidia)
1 coerulea
1 cyl indrospora
hyalospora
1 orchidis
r epens
spinosa
I t ieghemii
turkes tan ica
TILLETIOPSIS
lli lacina
SOURCE
FRI
C
FRI
SSSR
SSSR
SSSR
SSSR
SSSR
SSSR
SSSR
SSSR
FRI
SUBSTRATE
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
no specific subs t ra te - used in mixed cul ture
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3 ,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
REACTION
6j3-OH
17a-OH
2/3-OH
l l a -OH; l l j 3 -OH; 1 1 - C = 0 (via 110-OH)
l l a - O H
l l a - O H ; l l ß - O H
l l a - O H ; 11/3-OH; 1 1 - C = 0 (via l l ß - O H
11α-ΟΗ
11α-ΟΗ;11β-ΟΗ
11α-ΟΗ;11/3-ΟΗ
11α-ΟΗ;11]3-ΟΗ; 1 1 - C = 0 ( via 11/3-ΟΗ)
-
R E F .
S-849
W-1106; W-1107
S-849
E-224
E-224
E-224
E-224
E-224
E-224
E-224
E-224
S-849
664
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: TOMENTELLA
TORULA TORULOPSIS
TRAMETES TRICHODERMA
(BasidiOo - Agaricales) (Imperf. - Moniliales) (Imperf. - Moniliales) (Basidio. - Agaricales) (Imperf. - Moniliales)
SPECIES
TOMENTELLA
spec ies
TORULA
species
TORULOPSIS
ae r i a
Candida
TRAMETES
dickinsii
pini
TRICHODERMA
album (in mixed cul ture with Aspergi l lus niger [ l l a -OH] -Hende r son i a acicola [21-OH])
glaucum
SOURCE
FRI
NG
FRI
NRRL
IAM
LAM
MCC
LED (Z-696)
SUBSTRATE
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
5-choIesten-3ß-oI
24/3-methyl -5 ,7 ,22-choles ta-trien-3/3-ol
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21-d ihydroxy-4-pregnene-3,20-dione
4 -pregnene-3 ,20-d ione
17/3-hydroxy-4-androsten-3-one
21-hydroxy-4 -p regnene-3 ,20-dione
16a, 21 -dihydr oxy -4 -pregnene -3,20-dione
16a, 17a, 21 - t r ihydr oxy -4 -p reg -nene-3 ,20-d ione 16 ,17 -acetonide
REACTION
-
—
-
-
-
-
-
—
—
17a-OH
17/3-OH — not es te r if ied
21-OH — not e s t e r if ied
2 1 - O H -not es ter i f ied
21-OH — 21-OAc
R E F .
S-849
S-793c
S-793c
S-849
M-587
M-587
M-587
S-849
S-849
M-566
H-404
H-404
H-404
H-404
TABLE I I I
Transformat ions by Genus: TRICHODERMA
665
SPECIES
glaucum
(in mixed cul ture with 1 Cunninghamella
blakesleeana [11β-ΟΗ] 1 Wojnowicia g ramin i s
[21-OH])
1 koningi *
l ignorum 1 (in mixed cul ture with 1 Pénici l l ium adametz i
[ l i a -OH] Wojnowicia graminis [21-OH])
1 *
I n igrovi rens 1 (in mixed cul ture with 1 Hendersonia rubi
[21-OH] Stigmina platana[l l /3-OH])
1 spec ies
1 v i r ide
SOURCE
LED (Z-696)
MCC
SSSR (8,23)
(23)
MCC
SSSR ( 2 , 3 , 4 , 5 , 1 0 , 16,22)
MCC
NRRL
MCC
NRRL-2473
SUBSTRATE
11/3,16a, 17a, 21- te t rahydroxy-4-pregnene-3 ,20-d ione 16,17-acetonide
9a- f luoro- l l /3 ,16a , 17a, 21 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione
9 a - f l u o r o - l l ß , 16α, 17α, 2 1 - t e t r a -hyd roxy-4 -p regnene -3 ,20 -dione 16a, 17a-bora te (sodium salt)
9 a - f l u o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 - t e t r a -hydroxy-4 -p regnene -3 ,20 -dione 16,17-acetonide
9 a - f l u o r o - l l / 3 , 1 6 a , 1 7 a , 2 1 - t e t r a -h y d r o x y - l , 4 - p r e g n a d i e n e - 3 , 20-dione 16α, 17α-or thof or mate
9a- f luoro- l l /3 ,16a , 17a, 2 1 - t e t r a -hydroxy-1 ,4-pregnadiene -3 ,20-dione 16,17-acetonide
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4-pr e g n e n e - 3 , 1 1 , 2 0 - t r ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i b n e
4 -pregnene-3 ,20-d ione
plant saponins
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
REACTION
2 1 - O H -21-OAc
21-OH — not es ter i f ied
2 1 - O H -not es ter i f ied
2 1 - O H -21-OAc
2 1 - O H -not es ter i f ied
21-OH — 21-OAc
17a-OH
6/3,l la-diOH
17a-OH
17a-OH
6/3,1 la -d iOH
oxidation -products not identified
17α-ΟΗ
-
17α-OH
17α-OH
R E F .
H-404
H-404
H-404
H-404
H-404
H-404
M-566
T-1010
T-1010
M-566
T-1010
T-1010
M-566
K-478
M-565
D-185
666
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus: TRICHODERMA TRICHOLOMA
TRICHOMONAS (Basidio. - Agar icales) (Zoomastigina - Poiymastigina)
SPECIES
vir ide (in mixed cul ture with Curvular ia lunata [11/3-OH] Omphal ia t ra lucida [11/3-OH] and vVojnowicia graminis [17a-OH])
*
TRICHOLOMA
nudum
species
TRICHOMONAS (Protozoa)
foetus
SOURCE
NRRL-2473
PIRI (FA-3-1)
SSSR
NRRL-2371
AL (G-88)
NG
SUBSTRATE
4-pregnene-3 ,20-d ione
11/3-hydroxy-4-pr egnene -3 ,20 -dione
21-hydroxy-4 -p regnene-3 ,20-dione
4 -pregnene-3 ,20-d ione
3a-hydroxy-5ß-cholanic acid
4 -pregnene-3 ,20-d ione
4 -pregnene - 3 , 1 1 , 2 0 - t r i o n e
4 -pregnene-3 ,20-d ione
4 -pregnene-3 ,20-d ione
3 - h y d r o x y - l , 3 , 5 ( 1 0 ) - e s t r a t r i e n -17-one
17/3-hydroxy-4-estren-3-one
4 - e s t r ene -3 ,17 -d ione
l l / 3 -hyd roxy -4 -e s t r ene -3 ,17 -dione
4 - e s t r e n e - 3 , 1 1 , 1 7 - t r i o n e
3a -hydroxy- 5/3-androstan-17 -one
REACTION
17o-OH
17a-OH
17a-OH
11a-OH
oxidation
6/3,1 la -d iOH
17a-OH
oxidation -products not identified
oxidation -products not identified
oxidation -products not identified
1 7 - C = 0 -17/3-OH
17/3-OH — 1 7 - C = 0
1 7 - C = 0 - > 17/3-OH
1 7 - 0 = 0 - ^ 17/3-OH; Δ ; enol.
17-C = 0 -170-OH
1 7 - C = 0 - * 17/3-OH
R E F .
M-566; M-567
D-185
D-185
W-1119
W-1119
T-1010
T-1010
T-1010
R-778
S-825
S-829
S-829
S-830
S-830
S-830
S-830
T r a n s f o r m a t i o n s by Genus:
TABLE I I I
TRICHOMONAS
667
SPECIES
foetus
(in mixed cul ture with Corynebacter ium equi
1 (in mixed cul ture with 1 Corynebacter ium equi
1 gallinae
SOURCE
NG
NG
SUBSTRATE
3a-hydroxy-5/3-androstan-17-one aceta te
3/3-hydroxy-5-androsten-17-one
3/3-hydroxy-5-androsten-17-one ace ta te
17/3-hydroxy-4-androsten-3-one
11/3,17/3-dihydroxy-4-androsten-3-one
4 -andros tene -3 ,17-d ione
17ß -hyd roxy -4 -and ros t ene -3 ,11 -dione
l l a - h y d r o x y - 4 - a n d r o s t e n e - 3 , 1 7 -dione
l l / 3 -hydroxy-4 -andros t ene -3 ,17 -dione
4 -andr ostene - 3 , 1 1 , 1 7 - t r ione
l , 4 - a n d r o s t a d i e n e - 3 , 1 7 - d i o n e
4 -andros tene -3 ,17 -dione
4 - e s t r e n e - 3 , 1 1 , 1 7 - t r i o n e
3 - h y d r o x y - l , 3 , 5 (10) -es t ra t r i en-17-one
17/3-hydroxy-4-es t ren-3-one
4 -es t r ene -3 ,17 -dione
11/3-hydroxy-4-es t ren-3 ,17-dione
4 - e s t r ene - 3 , 1 1 , 1 7 - t r ione
3a - hydr oxy - 5/3-andr ostan -17-one
REACTION
1 7 - C = 0 -17/3-OH; 3 Q - O A C -*3a-OH
1 7 - C = 0 -17/3-OH
17-C = 0 ^ 17/3-OH; 3ß-OAc -3/3-OH
17/3-OH -1 7 - C = 0
17ß-OH -> 1 7 - C = 0
1 7 - C = 0 -17/3-OH
17/3-OH -1 7 - C = 0
1 7 - C = 0 -17/3-OH
1 7 - C = 0 17/3-OH
1 7 - C = 0 — 17/3-OH
1 7 - C = 0 - * 17/3-OH
1 7 - C = 0 - > 17/3-OH
1 7 - C = 0 -17/3-OH
1 7 - C = 0 -17/3-OH
17 /3 -OH^ 1 7 - C = 0
17-C = 0 -17/3-OH
1 7 - C = 0 — 17/3-OH; Δ1; enol.
1 7 - C = 0 ^ 17/3-OH
1 7 - C = 0 — 17/3-OH
R E F .
S-830
S-829; S-830
S-829
S-829
S-829
S-829
S-829
S-829
S-829
S-829; S-830
S-829
S-830
S-830
S-829; S-830
S-829
S-830
S-830
S-830
S-830
1
Δ
1
Δ
668
TABLE I I I
Transformat ions by Genus: TRICHOMONAS
SPECIES
gallinae
(in mixed cul ture with Corynebacter ium simplex [Δ1] )
(in mixed cul ture with Corynebacter ium equi [Δ1!)
vaginalis
SOURCE
NG
NG
SUBSTRATE
3a-hydroxy-5/3-androstan-17-one aceta te
3/3-hydroxy-5-androsten-17-one
3ß-hydroxy-5-andros ten-17-one aceta te
17/3-hydroxy-4-androsten-3-one
11/3,17/3-dihydr oxy-4-andr os ten-3-one
4 -androstene -3 ,17 -dione
17/3-hydroxy-4-andros tene-3 ,11-dione
1 l a -hydr oxy -4 -androstene - 3 , 1 7 -dione
l l / 3 -hydroxy-4 -andros tene -3 ,17-dione
4 - a n d r o s t e n e - 3 , 1 1 , 1 7 - t r i o n e
l , 4 - and ros t ad i ene -3 ,17 -d ione
4 - and ros t ene -3 ,11 ,17 - t r i one
11/3-hydroxy-4-androstene-3,17-dione
l l ß - h y d r o x y - 4 - e s t r e n e - 3 , 1 7 -dione
3a -hydr oxy - 5ß -andr ostan -17 -one
1,4 -andr ostadiene -3 ,17 -dione
REACTION
17-C = 0 - > 17/3-OH
1 7 - C = 0 - > 17/3 -OH
3/3-OAc->3/3-OH
1 7 - C = 0 - > 17/3-OH
1 7 - C = 0 -17/3-OH; 3ß-OAc -3/3-OH
17/3-OH -» 17-C = 0
17/3-OH-* 1 7 - C = 0
17-C = 0 -17/3-OH
17/3-OH^ 1 7 - C = 0
1 7 - C = 0 - > 17/3-OH
1 7 - C = 0 ^ 17/3 -OH
1 7 - C = 0 - * 17/3-OH
1 7 - C = 0 — 17/3-OH
1 7 - C = 0 - » 17/3-OH
1 7 - C = 0 — 17/3-OH
17-C = 0 - > 17/3-OH
17-C = 0 - > 17/3-OH
1 7 - C = 0 — 17/3-OH
R E F .
S-830
S-829
S-829
S-829; S-830
S-829
S-829
S-829
S-829; S-830
S-829
S-829; S-830
S-829; S-830
S-829; S-830
S-829
S-830
S-830
S-830
S-830
S-830
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by Genus : TRICOPHYTON (imperf. - Monmaies) TRICHOTHECIUM (Imperf. - Moniliales)
669
SPECIES
TRICOPHYTON
concentr icum
TRICHOTHECIUM (see Cephalothecium)
ar rhenopum
candidum
cystospor ium
domest icum
lute urn
SOURCE
FRI
uc
uc
CBS
C3S
CBS
SUBSTRATE
1 7a, 21 -dihydroxy -4 -pregnene -3,20-dione
4 -pregnene-3 ,20-d ione
1 Iß -hydroxy-4 -p regnene -3 ,20 -dione
21-hydroxy-4 -p regnene-3 ,20-dione aceta te
4 -p r egnene -3 ,11 ,20 - t r i one
4 -pregnene-3 ,20-d ione
11/3-hydroxy-4-pregnene-3,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione aceta te
4 -pregnene - 3 , 1 1 , 2 0 - t r ione
4 -p regnene-3 ,20-d ione
11/3-hydroxy-4-pregnene-3, 20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione aceta te
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
11/3-hydroxy-4-pregnene-3,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione aceta te
4 -pregnene - 3 , 1 1 , 2 0 - t r ione
4 -p regnene-3 ,20-d ione
11/3-hydroxy-4-pregnene-3,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione aceta te
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
REACTION
6/3-OH;l la-OH; 11/3-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
REF.
S-849
M-600
M-600
M-600
M-600
M-600
M-600
M-600
M-600
M-600
M-600
M-600
M-600
M-600
M-600
M-600
M-600
M-600
M-600
M-600
M-600
670
TABLE I I I
Transformat ions by Genus: T R I C H O T H E C I U M
SPECIES
plasmoparae
polybrochum
roseum
SOURCE
uc
uc
Armour and Co.
ATCC-8685
ATCC-12519
ATCC-12543 (QM-102E)
C
SUBSTRATE
4-pregnene-3 ,20-d ione
1 Iß -hydroxy-4 -p regnene -3 ,20 -dione
21-hydroxy-4 -p regnene-3 ,20-dione aceta te
4 -p r egnene -3 ,11 ,20 - t r i one
4 -pregnene-3 ,20-d ione
l l /3 -hydroxy-4-p regnene-3 ,20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione aceta te
4 -p r egnene -3 ,11 ,20 - t r i one
4 -pregnene-3 ,20-d ione ( t rea tment of nut r ien ts ; s ter i l iza t ion withH202 -use of cata lase)
9ce-fluoro-11/3, 21-dihydroxy-4-pregnene-3 ,20-d ione
9a - f luoro-21-hydroxy-1 ,4 -pr egnadiene - 3 , 1 1 , 2 0 - t r i o n e
3/3,14/3-dihydroxy-5/3-20(22)-cardenolide
21 -hydroxy-4 -p regnene-3 ,20-dione
17a, 21 -dihydroxy -4 -pregnene - 3 , 20-dione
17a ,21-d ihydroxy-4-pregnene-3 , 20-dione
21-hydroxy-4-p regnene-3 ,20-dione
l l /3 ,21-d ihydroxy-4-pregnene-3,20-dione
REACTION
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
11a-OH
17a-OH
17a-OH
7ß-OH
l i a - O H 16
Δ
11/3-OH
11a-OH
11/3-OH
11/3-OH
6/3-OH
17a-OH
6/3-OH
17a-OH
17a-OH; 11/3-OH - + i i - c = o
R E F .
M-600
M-600
M-600
M-600
M-600
M-600
M-600
M-600
W-1122
N-668
N-668
T-1013
T-1013
T-1013
T-1003
T-1003
T-1003
S-878
M-584
M-584
N-654
M-584
F-584
TABLE I I I
T ransformat ions by Genus: T R I C H O T H E C I U M
671
SPECIES
roseum
(in mixed cul ture with Cunninghamella blakesleeana [ l l ß - O H ; l l - C = O v i a l l ß - O H ] Ophiobolus he rpo-t r i chus L21-OH) and Rhizopus n igr icans [ l la-OH])
(in mixed cul ture with Calonectr ia decora [Δ1] Curvular ia lunata [11/3-OH] and Didymella iycopers ic i [A'I) (in mixed cul ture with
1 Ophiobolus herpo-t r i chus [21-OH])
1 (in mixed cul ture with 1 Calonectr ia decora
ιΔ;ι1 Ophiobolus herpo-t r i chus [21-OH|)
(in mixed cul ture with 1 Cunninghamella
blakesleeana [ l l ß - O H ; l l - C = 0 - v i a l l ß - O H ] )
(in mixed cul ture with 1 Calonectr ia decora
[Δ1 ] Cunninghamella blakesleeana [ 11/3-OH; 1 1 - C = 0 - v i a l lß -OH])
1 (in mixed cul ture with 1 Cunninghamella
blakesleeana [ l l ß -OH; l l - C = 0 - v i a l l ß -OH] )
(in mixed cul ture with Didymella Iycopersici [A1] )
(in mixed cul ture with Ophiobolus he rpo-t r i chus [21 -OH]
1 Wojnowicia graminis [21-OH] )
SOURCE
C
SUBSTRATE
21-hyd roxy -4 -p regnene -3 ,11 ,20 -t r ione
d , l - l l ß , 2 1 - d i h y d r o x y - 3 , 2 0 -diketo -4 -pr egnen -18 -al (18—»11) hemiace ta l
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
l l ß - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
l l ß - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
l l ß - h y d r o x y - 4 - p r e g n e n e - 3 , 20-dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
21 -hydroxy-4 -p regnene -3 ,20 -dione
d, 1-21-hydroxy-4-pregnene-3,2C-dione
21-hydroxy-9ß, l l ß - o x i d o - 4 -pregnene-3 ,20-d ione ace ta te
9 o - f l u o r o - l l ß , 2 1 - d i h y d r o x y - 4 -p regnene-3 ,20-d ione 2 1 -aceta te
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r i o n e
REACTION
17a-OH
d,l->d-17a-OH + 1
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
d , l - d - 1 7 a - O H + 1
17a-OH
17a-OH
17a-OH
R E F .
M-584
W-1102
W-1106
W-1107
W-1106
W-1106
W-1107
W-1106
W-1107
W-1102
W-1107
W-1107
W-1106
672
TABLE I I I
Transformat ions by Genus: TRICHOTHECIUM
SPECIES
ro seum (in mixed cul ture with Cunninghamella blakesleeana [11/3-OH; 1 1 - C = 0 ] Ophiobolus herpotr ichus [21-OH|)
(in mixed cul ture with Ophiobolus herpo-t r ichus [21-OH])
(in mixed cul ture with Ophiobolus he rpo-t r ichus [21-OH])
(Link) (also pseudovert ic i l l ium for m)
(= Cephalothecium roseum - ATCC-8685)
SOURCE
C
CBS
FRI
NRRL
NRRL-1665
SUBSTRATE
1,4 -pregnadiene -3 ,20-dione
1 Iß -hydroxy-1,4-pregnadiene -3,20-dione
1,4 -pregnadiene - 3 , 1 1 , 2 0 - t r ione
4 -pregnene-3 ,20-d ione
11ß-hydroxy-4-pregnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione aceta te
4 - p r e g n e n e - 3 , l l , 2 0 - t r i o n e
3/3,14/3-dihydroxy-5j3-20(22)-cardenolide
17a, 21-d ihydroxy-4-pregnene-3,20-dione
Sarsasapogenin
Diosgenin
4 -dehydr otigogenone
4 -pregnene-3 ,20-d ione
l l j3 -hydroxy-4-pregnene-3 ,20-dione
21-hydroxy-4 -p regnene-3 ,20-dione aceta te
11/3,21-dihydroxy-4-pr egnene -3, 20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
4 - p r e g n e n e - 3 , 1 1 , 2 0 - t r ione
REACTION
17a-OH
17«-OH
17a-OH
17a-OH
17a-OH
17a-OH
17a-OH
3 ß - O H - 3 - C = 0
7/3-OH
12j3-OH
-
---
17a-OH
17a-OH
6ß,17a-diOH; 21-OAc^21-OH
l l a , 1 7 a - d i O H ; 21-OAC—21-OH
17a-OH;ll /3-OH -n-c=o l l a - O H
17a-OH
R E F .
W-1106
W-1106
W-1106
M-600
M-600
M-600
M-600
J-432
J-432
J-432
S-849
M-587
M-587
M-587
M-600
M-600
M-600
M-600
M-600
M-600
M-600
673
T r a n s f o r m a t i o n s by Genus:
TABLE I I I
TRICHOTHECIUM TRITIRACHIUM
TUB ARIA UNIDENTIFIED
TAXONOMY
(Imperf. - Moniliales) (Basidio. - Agaricales)
SPECIES
roseum
TRITIRACHIUM
purureum
TUBARIA
conspersa
UNIDENTIFIED (listed alphabetically by reference)
1 bacter ium
SOURCE
NRRL-1665
NRRL-2576 (QM-936)
NRRL-2577 (QM-599)
SQ
SSSR (s t ra ins 17 through 26)
V E 3
FRI
AL(SS-32)
SCH (FC-C-78)
SUBSTRATE
21 -hyd roxy -4 -p regnene -3 ,11 ,20 -t r ione
4 -p regnene-3 ,20-d ione
4 -p regnene-3 ,20-d ione
6 a - c h l o r o - 1 6 a , 1 7 a , 2 1 - t r i -hydroxy-4 -p regnene -3 ,20 -dione 16,17-acetophenonide
6 a - f l u o r o - 1 6 a , 1 7 a , 2 1 - t r i -hyd roxy-4 -p regnene -3 ,20 -dione 16 ,1 7 -acetonide
4 -pregnene-3 ,20-d ione
1 l a - h y d r o x y - 4 - p r e g n e n e - 3 , 2 0 -dione
4 -pregnene - 3 , 1 1 , 2 0 - t r ione
4 - p r e g n e n e - 3 , 20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
4 -p regnene-3 ,20-d ione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
11/3,17a, 21 - t r i hyd roxy-4 -p reg -n e n e - 3 , 20-dione
17a, 21 -d ihydroxy-4-pregnene-3 , 1 1 , 2 0 - t r ione
REACTION
17a-OH
l l a , 1 7 a - d i O H
l l a , 1 7 a - d i O H
11a-OH
11a-OH
6/3,1 la -d iOH
l l a , 1 7 a - d i O H
-
-
6j3,14a-diOH
-
oxidation -products not identified
2 0 - C = O -20/3-OH
20-C=O-+ 20/3-OH
2 0 - C = O ^ 20/3-OH
R E F .
M-600
D-188
D-188
D-159
D-159
T-1010
T-1010
T-1010
T-1010
S-811
S-849
S-825
C-110
C-110
C-110
SPECIES
bac ter ium (listed alphabetically by reference)
(actually g ram + coccus . )
bac ter ium isolated from yeas t cake
"faulnis bac té r i en" (putrefactive -anaerobic)
intest inal mic roorgan-1 i s m s 1 (from male albino 1 r a t s )
SOURCE
SCH (FC-C-78)
Univ. of Milan
(IK; IKC; IKR 0 - 4 , Y-12)
Okayama Univ. Med.
School (CE-1)
NG
TAKEDA (A,B,C)
NG
NG
NG
SUBSTRATE
l l / 3 , 1 7 a , 2 1 - t r i h y d r o x y - l , 4 -pregnadiene-3 ,20-d ione
1 7 a , 2 1 - d i h y d r o x y - l , 4 - p r e g n a -d i ene -3 ,11 ,20 - t r i one
5-cholesten-3/3-ol
4 -cholesten - 3 -one
choles teryl acetate
3a, la, 12a-trihydroxy-5/3-cholanic acid (sole carbon source)
not given
11/3 ,17a ,21- t r ihydroxy-4-preg-nene-3 ,20-d ione
3/3 -hydr oxy - 5 -andr osten -17 -one (product then reduced by yeas t - 17-C = 0 -»17/3-OH -to t e s tos te rone - 17/3-hydroxy -4-andros ten-3-one)
17a -methyl - 5 -andros tene -3/3,17/3-diol
3/3-hydroxy-5-pregnen-20-one
5-choles ten-3ß-ol
5a -andros tane -3 ,17-d ione
17/3-hydroxy-4-androsten-3-one
4 -andros tene -3 ,17-d ione
5-choles ten-3a-o l
5-cholesten-3/3-ol
5 -choles ten-3 -one
4 ,4-dimethyl-5-choles ten-3/3-ol
5,7-cholestadien-3/3-ol
24-ethyl-5 ,22-choles tadien-3/3-ol
REACTION
2 0 - C = O -20/3-OH
2 0 - C = O ^ 20/3-OH
utilization
utilization
util ization
3 a - O H - 3 - C = 0 ; Δ4
1
Δ 1
Δ ; further oxidation
Δ ^ Δ ;3/3-OH ->3-C=0
Δ5—Δ4; 3β-ΟΗ - 3 - C = 0
Δ5—Δ4; 3/3-OH ->3-C=0
-
3-C = 0 ^ 3 a - O H ; 3-C = 0^3/3-OH
Δ ^ 5 / 3 - Η ; 3 - C = 0 - 3 a - O H
Δ4—5a-H; 3-C = 0-+3/3-OH
Δ4->5α-Η
Δ 5 - 5 β - Η ; 3a-OH-3/3-OH
Δ 5 ^ 5 β - Η
Δ 5 -5/3-Η; 3-C = 0—3ß-OH
-
Δ ^ 5 / 3 - Η
Δ5^5/3-Η
REF.
C-110
C-110
C-136
C-136
C-136
E-194; H-357
H-387
1-427
M-538
M-542
M-540
M-540
M-548
M-547; M-548
M-547; M-548
M-547
N-655
N-655
N-655
N-655
N-655
N-655
T r a n s f o r m a t i o n s by Genus :
TABLE I I I
UNIDENTIFIED
674
TABLE I I I
T ransformat ions by Genus: U N I D E N T I F I E D
675
SPECIES
intestinal microorgan-isms (from male albino rats)
bacteria - (22 isolates from 10 different source materials)
(cholesterol - sole carbon source)
(particularly active bacterium no. 5)
1 basidiomycete (MEX - 25,° 228)
bacterium (feces)
1 soil microorganisms
SOURCE
NG
NG
AL (SS-70) (SS-50)
AL (Z-9;12)
NG
NG
SUBSTRATE
24/3-methyl-5,7,22-cholesta-trien-3/3-ol
3α, 7α, 12a-trihydroxy-5ß-cholanic acid
l,3,5(l0)-estratriene-3,17ß-diol
1,3, 5(10)-estratriene-3,16a, 17/3 -triol
17ß-hydroxy-4-androsten-3-one
3/3 -hydr oxy - 5 -andr osten -17 -one
4-pregnene-3,20-dione
5-cholesten-3ß-ol
5-cholesten-3ß-ol acetate
5-cholesten-3/3-ol palmitate
24/3 - methyl -5,7,22 -cholesta -trien-3/3-ol
3a-hydroxy-5/3-cholanic acid
3a, 6a-dihydroxy-5/3-cholanic acid
3a, 12a-dihydroxy-5/3-cholanic acid
3a, 7a, 12a-trihydroxy-5ß-cholanic acid
4-pregnene-3,20-dione
4-pregnene-3,20-dione
5-cholesten-3ß-ol
potassium 5a-cholestan-3ß-ol sulfate
REACTION
Δ5-5β-Η
7a-OH->7-C = 0
7a-OH - H
12a-OH->12-C = 0;7a-OH-*H
3a-OH-3-C=0; 12a-OH^12-C = 0;7a-OH--»H
utilization
utilization
utilization
—
utilization
utilization
-
—
utilization
—
—
utilization
oxidation -products not identified
oxidation -products not identified
Δ5-5β-Η
A ring cleavage
REF.
N-655
N-676
N-676
N-676
N-676
S-793c
S-793c
S-793c
S-793c
S-793c
S-793c
S-793c
S-793c
S-793c
S-793c
S-793c
S-793c
S-793c
S-825
S-825
S-914
S-940
676
TABLE I I I TAXONOMY
T r a n s f o r m a t i o n s by G e n u s : UNIDENTIFIED USTILAGO VENTURIA
VERTICILLIUM
(Basidio. - Usti laginales) (Asco. - Sphaeriales) (Imperf. - Moniliales)
SPECIES
soil mic roorgan i sms
bac ter ia (soil)
fungus belonging to family - Dematiaceae
fungus belonging to order - Melanconiales and Moniliales
USTILAGO
zeae
VENTURIA
p i rma (pirina)
VERTICILLIUM
a lbo-a t rum
dahliae
malthousii
SOURCE
NG
NG
NG
Lepetit
NG
NRRL
TNAES
IFO (5922)
IFO (5916; 6119; 6126; 6150)
IFO (6624)
SUBSTRATE
5-cholesten-3j3-ol
potass ium 5-cholesten-3/3-ol sulfate ( subs t ra te used to diver t attack from 3-C position)
5-cholesten-3/3-ol ( subs t ra te added to soil to demonst ra te degradation is the r e su l t of microbia l action)
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-d ihydroxy-1 ,4 -p regna-d iene-3 ,20-dione
3j3-hydroxy-5-pregnen-20-one
Sarsasapogenin
Diosgenin
4 -dehydrotigogenone
17a, 21-dihydroxy-4-pregnene -3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
17a, 21-dihydroxy-4-pregnene-3,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
REACTION
Δ 5 - Δ 4 ; 3j3-OH ->3-C=0
7-C = 0 (probably not microbiological)
utilization
2 0 - C = O -20/3-OH
l l a - O H
11/3-OH
14a-OH
Δ -»Δ*; 3β-ΟΗ - 3 - C = 0
-
-
-
-
—
—
6j3-OH
l l a - O H
R E F .
S-940
S-940
T-1029
V-1045
T-990
T-990
T-990
P-710
M-587
M-587
M-587
S-849
K-468
K-468
K-468
K-468
677
TABLE I I I TAXONOMY
τ . . . . η VERTICILLIUM T r a n s f o r m a t i o n s by G e n u s : VIBRIO (Schizo. - Pseudomonadaies)
VOLUTELLA (Imperf. - Moniliaies) vVOJNOWICIA (Imperf. - Sphaeropsidales)
SPECIES
nieveost ra tosum
species
theobromae
(in mixed cul ture with Bacil lus sphaer icus -ATCC-7C55 [ Δ 1 ] )
VIBRIO
cyclosi tes
metschnikovu
percolans
(but in mixed culture with Mycococcus sp . A,)
tyrogenes
VOLUTELLA
ciliata
WOJNOWICIA
graminis
(in mixed culture with 1 Trichothecium r o s e u m
[ 1 7 a - O H ] )
SOURCE
FRI
IFO (6625)
NG
CBS
NG
IAM
IFO (3348)
IAM
Leo P h a r m , P r o d u c t s , Denmark
C
SUBSTRATE
17a, 21-dihydroxy-4-pregnene -3,20-dione
1 7a, 21 -dihydroxy -4 -pregnene -3,20-dione
5-cholesten-3/3-ol (sole carbon source)
24 /3-methyl -5 ,7 ,22-choles ta t r ien-3/3-ol (sole carbon source)
17a, 21-dihydroxy-4-pregnene -3,20-dione
5-cholesten-3/3-ol (sole carbon source)
17a, 21-dihydroxy-4-pregnene -3,20-dione
11/3,17a, 21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
17a, 21 -dihydroxy-4-pregnene -3 ,20-dione
17/3-hydroxy-4-androsten-3-one
17j3-hydroxy- 17a -methyl - 4 -andros ten-3-one
17a, 21 -dihydr oxy-4-pregnene-3,20-dione
d, l - l l ^ - h y d r o x y - 3 , 2 0 - d i k e t o - 4 -pregnen-18-o ic acid ( 18—^ 11) lactone
d, i - l l / 3 -hydroxy-4 -p regnene-3 , 18 ,20- t r ione
REACTION
-
6/3-OH
-
—
11a-OH
11/3-OH
11a-OH; l l ß - O H
-
—
1
Δ
—
1
Δ 1
Δ
1
Δ
d , l - d - 2 1 - O H + 1
d , l >d-21-OH +1
R E F .
S-849
K-468
S-793c
S-793c
K-468
K-468
K-468
T-1030
S-849
1-428
1-428
S-849
L-525
L-525
L-525
W-1102
W-1102
678
TABLE I I I
Transformat ions by Genus: WOJNOWICIA
SPECIES
graminis
(in sequential fe rmen-tation with one or the other of Curvular ia lunata [110-OH] Tr ichoderma [17a-OH] Cunninghamella [11/3-OH] Pénic i l l ium [ l l a -OH]Ompha l i a t r a
1 [11/3-OH])
SOURCE
CBS
NRRL -2472
SUBSTRATE
17/3-hydroxy-4-androsten-3-one
4 -andros tene-3 ,17-d ione
4-pregnene-3 ,20-d ione
4-pregnene-3 ,20-d ione
1 l a -hyd roxy -4 -p regnene -3 ,20 -dione
11/3-hydr oxy-4-pr egnene-3 ,20-dione
17a-hydroxy-4-pregnene-3 ,20-dione
17a, 21 -d ihydroxy-4-pregnene-3,20-dione
11/3,12/3-oxido-4-pregnene-3,20-dione
11/3,120-oxido-1,4-pregnadiene-3,20-dione
4-pregnene-3 ,20-d ione
REACTION
6/3-OH
12a-OH
14a -OH ;17/3 -OH - 1 7 - C = 0
16a-OH
16j3-OH
1 6 - C = 0
17/3-OH -1 7 - C = 0
14 Δ ; 12a-OH
16a-OH; Δ -» 5£-H;3-C = 0 ?
6/3-OH
1 7 - C = 0 -17/3-OH
16a-OH;17-C=0 -17/3-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
21-OH
R E F .
H-381
H-381
H-381
H-381
H-381
H-381
H-381
H-381
H-381
H-381
H-381
H-381
M-564
D-183; D-184
D-183; D-184
D-184
D-184
D-184
D-156; D-157
D-157
M-566; M-567
TABLE I I I
679
TAXONOMY
T r a n s f o r m a t i o n s by Genus: W O J N O N V I C I A XANTHOMONAS XEROMPHALINA
XYLARIA YEAST
(Schizo. - Pseudomonadales) (Basidio. - Agar icales) (Asco. - Sphaeriales)
SPECIES
gramin is (in sequential f e rmen-tation with Curvular ia lunata[l l j3-OH])
XANTHOMONAS (see Phytomonas)
c i t r i
malvacerum
(in mixed cul ture with Mycococcus sp . Ax)
XEROMPHALINA
tenuipes
XYLARIA
1 polymorpha
1 species
YEAST
see under the following genera;
CANDIDA DE3ARYOMYCES ENDOMYCES EREMASCUS HANSENULA KLOECKERA MONILIA NADSONIA OÏDIUM OOSPORA PICHIA PSEUDOMYCODERMA RHODOTORULA
1 (continued)
SOURCE
NRRL-2472
FAKU
IFO (3383)
AL (SS-6)
FRI
Sear le (M-40-6)
SUBSTRATE
17a-hydroxy-4-p regnene-3 ,20-dione
17a ,21-d ihydroxy-4-pregnene-3,20-dione
l l ß , 17a ,21 - t r i hyd roxy-4 -p reg -nene-3 ,20-d ione
4-pregnene-3 ,20-d ione
17a, 21 -dihydroxy-4-pregnene -3,20-dione
4 -andr ostene -3 ,17 -dione
REACTION
21-OH
l
Δ
-
—
oxidation -products not identified
I I G - O H
1/3-OH
7/3-OH
15/3-OH
1/3,6/3-diOH
R E F .
M-566; M-567
S-849
1-428
1-428
S-825
S-849
D-165
D-165
D-165
D-165
680
T r a n s f o r m a t i o n s by Genus:
TABLE I I I TAXONOMY
YEAST ZYGORHYNCHUS (Phyco, - Mucorales)
SPECIES
see under the following genera:
SACCHAROMYCES SACCHAROMYCODES SPOROBOLOMYCES TORULA TORULOPSIS ' *
ZYGORHYNCHUS
heterogamus
moel ler i
SOURCE
SSSR
U
SSSR
U
SUBSTRATE
17a ,21-d ihydroxy-4-pregnene-3,20-dione
4-pregnene-3 ,20-d ione
17a-hydroxy-4-pregnene-3 ,20-dione
21-hydroxy-4-p regnene-3 ,20-dione
17ö,21-d ihydroxy-4-pregnene-3, 20-dione
17o,21-dihydroxy-4-pregnene-3,20-dione
4-pregnene-3 ,20-d ione
17a-hydroxy-4-pregnene-3 ,20-dione
21-hydroxy-4-p regnene-3 ,20-dione
17a, 21 -dihydroxy -4 -pregnene -3,20-dione
REACTION
6/3-OH;lla-OH
oxidation
oxidation
oxidation
oxidation
6/3-OH
oxidation
oxidation
oxidation
oxidation
R E F .
E-224
M-601; M-636
M-601; M-636
M-601; M-636
M-601; M-636
E-224
M-601; M-636
M-601; M-636
M-601; M-636
M-601; M-636
CHAPTER VI
BIBLIOGRAPHY
Adams, W. J . , Patel , D. K. , Petrow, V . , and Stuart-Webb, I. A. , J. Chem. Soc . , p. 297 (1956).
Agnelle-, E. J . , Bloom, B. M. , and Laubach, G. D . , J. Am. Chem. Soc. 77, 4684 (1955).
Agnello, E. J . , Bloom, B. M . , and Laubach, G. D . , U .S . Patent 2,835,683 (May 20, 1958) .
Agnello, E. J . , Bloom, B. M . , and Laubach, G. D . , U .S . Patent 2 ,835,684 (May 20, 1958).
Agnello, E. J. , Bloom, B. M . , and Laubach, G. D . , U .S . Patent 2 ,976 ,283 (March 21 , 1961).
Agnello, E. J . , Figdor, S. K. , Hughes, G. M. K. , Ordway, H. W. , Pinson, R . , J r . , Bloom, B. M . , and Laubach, G. D . , J. Org. Chem. 28, 1531 (1963).
Agnello, E. J . , Laubach, G. D . , and Moreland, W. T . , U .S . Patent 3 ,067,197 (December 4 , 1962).
Allen, W. S . , Bernstein, S . , Feldman, L. I. , and Weiss , M. J . , J. Am. Chem. Soc. 82, 3696 (1960).
Allen, W. S . , and Feldman, L. I . , U .S . Patent 3 ,010,877 (November 28, 1961).
Amiard, G. , andHeymes , R . , U .S . Patent 3 ,005 ,816 (October 24, 1961).
Amiard, G. , and Heymes, R . , U .S . Patent 3 ,033 ,863 (May 8, 1962).
Amiard, G. , andHeymes , R . , U .S . Patent 3 ,052 ,697 (September 4 , 1962).
Amiard, G . , Heymes, R . , and Thuong, T. V. , U .S . Patent 3 ,081 ,300 (March 12, 1963).
Arnaudi, C . , Boll . Sez. Ital. Soc. Intern. Microbiol. 11 , 208 (1939).
Arnaudi, C . , Boll . 1st. Sieroterap. Milan. 21 , 1 (1942).
Arnaudi, C . , Zentr. Bakteriol . , Parasi tenk. , Abt. I. Orig. 105, 352 (1942).
Arnaudi, C . , Boll . 1st. Sieroterap. Milan. 21 , 1-12 (1942).
Arnaudi, C . , Experientia 2 , 138 (1946).
Arnaudi, C . , Rend. Ist. Lombardo Sei. Lettere, Pt. I 83, 151-164 (1950).
Arnaudi, C . , Experientia 7, 81 (1951). REVIEW.
Arnaudi, C. , Appl. Microbiol. 2 , 274 (1954). REVIEW.
Arnaudi, C. , and Colla, C . , Experientia 5, 120 (1949).
681
References A-l through Z-1134 are included in this chapter.
A - l
A-2
A-3
A-4
A-5
A-6
A-7
A-8
A-9
A-10
A - l l
A-12
A-13
A-14
A-15
A-16
A-17
A-18
A-19
A-20
A-21
A-22
682 VI. BIBLIOGRAPHY
Arnaudi, C . , and Ercol i , A. , Boll. 1st. Sieroterap. Milan. 20, 137 (1941).
Arth, G. E . , Beyler , R. E . , and Sarett, L. H . , U .S . Patent 3 ,004,994 (October 17, 1961).
Arth, G. E . , Beyler , R. E . , and Sarett, L. H . , U.S . Patent 3 ,054 ,811 (September 18, 1962).
Asai , T . , Aida, K. , Ohki, E . , Tanaka, T . , and Hattori, M . , J. Agr. Chem. Soc. Japan 32 , 723 (1958).
Asai , T . , Aida, K. , Tanaka, T . , Ohki, E . , Matsuhisa, T . , Takeda, Y . , and Inui, T. , J. Gen. Appl. Microbiol. (Tokyo) 5, 127 (1959).
Asai , T . , Aida, K. , Tanaka, T . , and Sato, Yoshihiro, J. Agr. Chem. Soc. Japan 35, 122 (1961).
Asai , T . , Tsuda, K. , Aida, K. , Ohki, E . , Tanaka, T . , Hattori, M . , and Machida, H . , J. Gen. Appl. Microbiol. (Tokyo) 4 , 63 (1958).
Asai , T . , Tsuda, K. , Aida, K. , Ohki, E . , Tanaka, T . , and Hattori, M . , J. Gen. Appl. Microbiol. (Tokyo), 4 , 79 (1958).
Ayer, D. E . , U .S . Patent 3 ,056 ,808 (October 2 , 1962).
Baba, S . , Brodie, H. J . , Hayano, M . , Peterson, D. H . , and Sebek, O. K. , Steroids l , 151 (1963).
Babcock, J. C . , and Campbell, J. A. , U .S . Patent 2 ,838,534 (June 10, 1958).
Babcock, J. C. , Campbell, J. A . , and Hogg, J. A . , U .S . Patent 2 ,838,531 (June 10, 1958).
Babcock, J. C . , Campbell, J. A . , Hogg, J. A . , and Sebek, O. K. , U .S . Patent 2 ,838,544 (June 10, 1958).
Babcock, J. C . , and Pederson, R. L . , U.S. Patent 2 ,971,886 (February 14, 1961).
Badia, D. J . , and Sardinas, J. L . , U .S . Patent 3 ,010 ,876 (November 28, 1961).
Bagli, J. P . , Morand, P. F . , Wiesner, K. , and Gaudry, R . , Tetrahedron Letters, p. 387 (1964).
Baichikov, A. G . , Barmenkov, A. S . , and Eroshin, V. K. , Med. Prom. SSSR 13, 15 (1959). REVIEW.
Barber, G. W. , Peterson, D. H . , and Ehrenstein, M . , J. Org. Chem. 25, 1168 (1960).
Barkemeyer, H. R . , Stoudt, T. H . , Chemerda, J. M . , Kozlowski, M. A . , and McAleer, W. J . , Appl. Microbiol. 8, 237 (1960).
Barmenkov, A. S. , Fedotiva, M. V . , Eroshin, V. K. , Gusakova, E. G . , and Ogareva, O. B . , Med. Prom. SSSR 15, 39 (1961).
Beal , P . F . , Hogg, J. A . , and Jackson, R. W., U .S . Patent 2 ,989,523 (June 20, 1961).
Beal, P . F . , and Kagan, F . , U.S . Patent 3 ,053 ,864 (September 11 , 1962).
Beesch, S. C. , and Shull, G. M . , Ind. Eng. Chem. 47 , 1857 (1955). REVIEW.
Beesch, S. C . , and Shull, G. M . , Ind. Eng. Chem. 4 8 , 1585 (1956). REVIEW.
Beesch, S. C . , and Shull, G. M . , Ind. Eng. Chem. 49 , 1491 (1957). REVIEW.
Beesch , S. C . , and Tanner, F . W . , Jr . , Ind. Eng. Chem. 50, 1341 (1958). REVIEW.
A-23
A-24
A-25
A-26
A-27
A-28
A-29
A-30
A-31
B-32
B-33
B-34
B-35
B-36
B-37
B-38
B-39
B-40
B-41
B-42
B-43
B-44
B-45
B-46
B-47
B-48
BIBLIOGRAPHY 683
Beesch , S. C. , and Tanner, F . W. , J r . , Ind. Eng. Chem. 51,1086(1959) . REVIEW.
Benetti, R. T . , Ann. Microbiol. 5, 1 (1952).
Berg, R. G . , and Laubach, G. D . , U . S . Patent 3 ,022,297 (February 20, 1962).
Bergstrom, C. G . , U .S . Patent 2 ,703,799 (March 8, 1955).
Bernhauer, K. , Ergeb. Enzymforsch. 11 , 219 (1944). REVIEW.
Bernstein, S. , and Allen, W. S . , U .S . Patent 2 ,806 ,043 (September 10, 1957).
Bernstein, S . , Allen, W. S . , Hel ler, M . , Lenhard, R. H . , Feldman, L. I . , and Blank, R. H . , J. Org. Chem. 24, 286 (1959).
Bernstein, S . , Feldman, L. I . , Allen, W. S . , and Blank, R. H . , U.S . Patent 2 ,962 ,512 (November 29, 1960).
Bernstein, S . , Feldman, L. I . , Allen, W. S . , Blank, R. H. , and Linden, C. E. , Chem. & Ind. (London), p. I l l (1956).
Bernstein, S . , Hel ler, M . , Feldman, L. I . , Allen, W. S . , Blank, R. H . , and Linden, C. E. , J. Am. Chem. Soc. 82, 3685 (1960).
Bernstein, S. , Lenhard, R. H . , and Allen, W. S . , U .S . Patent 2 ,789 ,118 (April 16, 1957).
Bernstein, S . , Lenhard, R. H . , Allen, W. S. , Heller, M . , Littell, R . , Stolar, S. M . , Feldman, L. I . , and Blank, R. H . , J. Am. Chem. Soc. 78, 5693 (1956).
Bernstein, S . , Lenhard, R. H . , Allen, W. S . , Heller, M . , Littell, R . , Stolar, S. M . , Feldman, L. I . , and Blank, R. H . , J. Am. Chem. Soc. 81 , 1689 (1959).
Bernstein, S. , Lenhard, R. H . , Rigler, N. E . , and Darken, M. A. , J. Org. Chem. 25, 297 (1960).
Blank, R. H . , Shay, A. J . , P r u e s s , L. M. , and Rigler, N. E. , U .S . Patent 2 ,982,695 (May 2 , 1961).
Bloom, B. M . , Hayano, M . , Saito, A . , Stone, D . , and Dorfman, R. I. , Federa-tion Proc. Ij5, 222 (1956).
Bloom, B. M . , Kita, D. A . , Laubach, G. D . , and Shull, G. M . , U .S . Patent 2 ,891,080 (June 16, 1959).
Bloom, B. M . , and Shull, G. M. , J. Am. Chem. Soc. 77, 5767 (1955).
Bodanszky, A . , Kollonitsch, J . , and Wix, G. , Experientia 11 , 384 (1955).
Bork, K. H . , Bruckner, K. , Mannhardt, H. J . , Metz, H . , and von Werder, F . , U .S . Patent 3 ,064 ,015 (November 13, 1962).
Bork, K. H . , Bruckner, K. , and Metz, H. , Naturwiss. 50, 42 (1963).
Bourgain, L . , Ph. D. Thes i s , University of Nancy, France (1956).
Bowers , A . , Casas-Campil lo, C. , and Djerass i , C . , Tetrahedron 2, 165 (1958).
Bowers , A . , Casas-Campil lo, C . , Zderic, J . A . , and Djerass i , C. , U .S . Patent 3 ,067 ,212 (December 4 , 1962).
Bowers , A . , Mil ls , J. S . , Casas-Campil lo, C . , and Djerass i , C . , J. Org. Chem. 27, 361 (1962).
Bowers , A . , and Ringold, H. J. , U .S . Patent 3 ,037 ,976 (June 5, 1962).
Bowers , A . , and Ringold, H. J . , U .S . Patent 3 ,050,534 (August 21 , 1962).
Brodie, H. J. , Hayano, M . , and Gut, M . , J. Am. Chem. Soc. 84, 3766 (1962).
B-49
B-50
B-51
B-52
B-53
B-54
B-55
B-56
B-57
B-58
B-59
B-60
B-61
B-62
B-63
B-64
B-65
B-66
B-67
B-68
B-69
B-70
B-71
B-72
B-73
B-74
B-75
B-75a
684 VI. BIBLIOGRAPHY
Bruckner, K. , Irmscher, Κ. , von Werder, F . , Bork, K. H . , and Metz, H . , Ber . 94, 2897 (1961).
Burn, D. , E l l i s , B . , and Petrow, V . , J. Chem. Soc . , p. 795 (1958).
Butenandt, A . , and Dannenberg, H. , Ber . 71 , 1681 (1938).
Butenandt, A . , and Dannenberg, H. , Naturwiss. 30, 52 (1942).
Butenandt, A . , Dannenberg, H . , and Sur any i , L. A . , Ber. 73 , 818 (1940).
Butenandt, A . , and Suranyi, L. A . , Ber. 75, 591 (1942).
Camerino, B . , Alberti, C. G . , and Vercellone, A . , Gazz. Chim. Ital. 83, 684 (1953).
Camerino, B . , Alberti, C. G . , and Vercellone, A . , Helv. Chim. Acta 36, 1945 (1953).
Camerino, B . , Alberti, C. G. , Vercellone, A . , and Ammannati, F . , Gazz. Chim. Ital. 84, 301 (1954).
Camerino, B . , and Modelli, R. , Gazz. Chim. Ital. 86, 1219 (1956).
Camerino, B . , Modelli, R . , and Spalla, C. , Gazz. Chim. Ital. 86, 1226 (1956).
Camerino, B . , and Sciaky, R. , Gazz. Chim. Ital. 89, 654 (1959).
Camerino, B . , and Vercellone, A . , Gazz. Chim. I ta l . , 86, 260 (1956).
Camerino, B. , and Vercellone, A . , U .S . Patent 2 ,866,736 (December 30, 1958).
Camerino, B . , and Vercellone, A . , U.S . Patent 2 ,880,141 (March 31 , 1959).
Campbell, J. A . , Babcock, J. C . , and Hogg, J. A . , U .S . Patent 3 ,004,044 (October 10, 1961).
Campbell, J. A . , Babcock, J. C . , and Wechter, W. J . , U .S . Patent 3 ,086 ,029 (April 1 6 , 1963).
Campbell, J. A . , Pederson, R. L . , Babcock, J. C . , and Hogg, J. A . , U .S . Patent 2 ,877,240 (March 10, 1959).
Canonica, L . , Pacini , N . , Scolastico, C . , and Valcavi, U . , Gazz. Chim. Ital. 93, 301 (1963).
Canonica, L . , Pacini , N . , Scolastico, C . , and Valcavi, U . , Gazz. Chim. Ital. 93, 787 (1963).
Canonica, L . , Valcavi, U . , and Scolastico, C . , Gazz. Chim. Ital. 93, 368 (1963).
Capek, A . , and Hanc, O . , Folia Microbiol. (Prague) 5, 251 (1960).
Capek, A . , and Hanc, O . , Folia Microbiol. (Prague) 6, 237 (1961).
Capek, A . , and Hanc, O . , Folia Microbiol. (Prague) 7, 121 (1962).
Capek, A . , and Hanc, O . , Folia Microbiol. (Prague) 7, 181 (1962).
Capek, A . , Hanc, O . , Kakâc, B . , and Tadra, M . , Folia Microbiol. (Prague) 7, 175 (1962).
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Capek, A . , Hanc, O. , and Pavlu, H . , Cesk. Mikrobiol. 2 , 168 (1957).
B-76
B-77
B-78
B-79
B-80
B-81
C-82
C-83
C-84
C-85
C-86
C-87
C-88
C-89
C-90
C-91
C-92
C-93
C-94
C-95
C-96
C-97
C-98
C-99
C-100
C-101
C-102
C-103
C-104
BIBLIOGRAPHY 685
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C-105
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C-121
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D ias s i , P . A . , Laskin , A. I . , and P r inc ipe , P . A . , U . S . Pa tent 3 ,060,176 (October 23 , 1962).
C-132
C-133
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C-141
D-142
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D-148
D-149
D-150
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D-152
D-153
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D-155
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D-157
BIBLIOGRAPHY 687
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D-161
D-162
D-163
D-164
D-165
D-166
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D-174
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D-181
D-182
D-182a
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D-184
D-185
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D-187
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Dodson, R. M.
Dodson, R. M.
Dodson, R. M.
Dodson, R. M.
Dodson, It. M.
Dodson, R. M.
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D-188
D-189
D-190
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D-192
D-193
E-194
E-195
E-195a
E-196
E-197
E-198
E-199
E-200
E-201
E-202
E-203
E-204
E-205
E-206
E-207
E-208
E-209
E-210
E-211
E-212
E-213
BIBLIOGRAPHY 689
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690 VI. BIBLIOGRAPHY
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F-257 Fried, J. , U .S . Patent 3 ,048 ,581 (August 7, 1962).
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F-259 Fried, J . , U.S. Patent 3 ,050 ,535 (August 21 , 1962).
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F-261 Fried, J . , U .S . Patent 3 ,053,837 (September 11 , 1962).
F-262 Fried, J . , U.S . Patent 3 ,069 ,418 (December 18, 1962).
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F-267 Fried, J. , Perlman, D. , Langlykke, A. F. , and Titus, E. O . , U.S . Patent 2 ,855,343 (October 7, 1958).
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F-269 Fried, J. , and Thoma, R. W. , U.S . Patent 2 ,744,120 (May 1, 1956).
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F-272 Fried, J. , and Thoma, R. W. , U .S . Patent 2 ,793,164 (May 21, 1957).
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CHAPTER VII
BIBLIOGRAPHICAL APPENDIX
References Ap-1 through Ap-100 are included in this chapter.
Ap-l Afonso, A. , Herzog, H. L. , Federbush, C. , and Charney, W. , Steroids 7, 429 (1966). Conversion of 1,3,5(10) - cholestatrien-3-ol into estrone by Nocardia restr ictus.
Ap-2 Bellet , P . , Nomine, G. , and Mathieu, J. , Compt. Rend. 263C, 88 (1966). Stereo-specific reduction of an optically inactive ketonic precursor in a total synthesis of steroids using Rhizopus arrhizus to give an optically active intermediate which could be converted to estradiol of the natural s e r i e s . Same principle as Gibian reference (Ap-24).
Ap-3 Benn, W. R. , Tiberi, R. , and Nussbaum, A. L. , J. Org. Chem. 29, 3712 (1964). Oxidation of 5,16-pregnadiene-3/3,20/3-diol and the corresponding 20a-o l with Flavo-bacterium dehydrogenans to 16-dehydroprogesterone.
Ap-4 Bolt, C. C. , Mijs, W. J. , Zeelen, F. J. , Szpilfogel, S. A . , de Fl ines , J. and van der Waard, W. F . , Rec. Trav. Chim. 84, 626 (1965). lj3-Hydroxylation of 19-nortestosterone with Botryodiplodia malorum.
Ap-5 Brannon, D. R. , Martin, J. , Oehlschlager, A. C. , Durham, N. N. , and Zalkow, L. H . , J. Org. Chem. 30, 760 (1965). Aspergillus tamarii on progesterone gave testololactone and 11/3 -hydroxytestosterone. 11/3-Hydroxyprogesterone gave 11/3-hydroxytestosterone. l la-Hydroxyprogesterone gave 11a-hydroxytestosterone. 4-Androstene-3,17-dione and testosterone gave testololactone.
Ap-6 Bridgeman, J. E. , Cherry, P. C . , Cottrell , W. R. T . , Jones , E. R. H . , Le Quesne, P. W. , and Meakins, G. D . , Chem. Commun, p. 561 (1966). 1/3,6a-Dihydroxylation of 5a-androstan-17-one with unnamed organism.
Ap-7 Canonica, L. , Jommi, G. , Pagnoni, U. M . , Pel l izzoni , F . , Ranzi, B. M. , and Scolastico, C . , Gazz. Chim. Ital. 96, 820 (1966). 7j3-Hydroxylation and oxidation of 3-hydroxyl to ketone in glycyrrhetic acid by Curvularia lunata.
Ap-8 Capek, A . , Hanc, O . , Tadra, M . , and Tuma, J. , Cesk. Farm. 4 , 198 (1966). Improved preparation of cortisone from Re ichs tem^ Compound S.
Ap-9 Capek, A . , Tadra, M . , and Tuma, J . , Folia Microbiol. (Prague) 9, 380-382 (1964).
Ap-10 Casas-Campil lo, C. , and Baut is ta, M . , Appl. Microbiol. 13 , 977 (1965). 1 5 a -Hydroxylation of estrone and estradiol with Fusarium moniliforme. 6/3-Hydroxyla-tion of estradiol 3-methyl ether with same organism.
Ap-11 Casas-Campil lo , C . , Esparza, F . , and Balandrano, D . , Bacteriol . Proc . p. 93 (1965).
Ap-12 Cherry, P. C . , Jones , E. R. H . , and Meakins, G. D . , Chem. Commun, p. 587 (1966). 3/3-Hydroxylation and 12/3-hydroxylation of 5-androsten-7-one by Calonectria decora. Tentative 4j3-hydroxylation of the same substrate by the same organism.
721
722 VII. BIBLIOGRAPHICAL APPENDIX
Ap-13 Coombe, R. G. , Tsong, Y. Y. , Hamilton, P. B. , and Sih, C. J. , J . Biol. Chem. 241, 1587 (1966). Degradation of estrone by Nocardia sp. via 4-hydroxylation.
Ap-14 Curtis, P. J . , Biochem. J. 97, 148 (1965). Demethylation of totally-synthetic, phenolic 8-azasteroid 3-methyl ether by Aspergillus flavus and Cunninghamella blakesleeana. Reduction of 17a-carbonyl group in same substrate to 17aa-ol and 17a/3-ol by Aspergillus ochraceus.
Ap-15 Davidson, S. J . , and Talalay, P. , J . Biol. Chem. 241, 906 (1966). Soluble 5/3-dehydrogenase from Pseudomonas testosteroni.
Ap-16 deFlines, J . , van der Sijde, D. , and van der Waard, W. F. , Rec. Trav. Chim. 85, 701 (1966). Fermentation of 9/3,10α -progesterone with Sporomia pollaccii yielded mainly 9/3,10a -testosterone. Fermentation with Helicosporium lumbricopsis afforded 9j3, 10α? -androst-4-ene-3,17-dione. Fermentation with Colletotrichum gloeosporioides afforded 15a-hydroxy-9/3,10a-progesterone. This product was converted with Helicosporium lumbricopsis to 15a-hydroxy-9/3,10a-androst-4-ene-3,17-dione. Fermentation of 6-dehydro-9/3,10α-progesterone with Mastigosporium heterosporium afforded 9/3,10a-androsta-4,6-diene-3,17-dione.
Ap-17 Deghenghi, R. , Revesz, C. , and Gaudry, R. , J . Med. Chem. £, 301 (1963). Failure of Septomyxa affinis and Streptomyces lavendulae to degrade the side chain to 17a-alkyl derivatives of progesterone.
Ap-18 Dodson, R. M. , Langbein, G. , Muir, R. D. , Schubert, A. , Siebert, R. , Tamm, C , and Weiss-Berg, E. , Helv. Chim. Acta 48, 1933 (1965). Identity of "6/3,15α·-di-hydroxyprogesterone" (G-319) and " l i a , 15/3-dihydroxyprogesterone" (M-596) with 12/3,15α -dihydroxyprogesterone.
Αρ-19 El-Tayeb, O. , Knight, S. G. , and Sih, C. J . , Biochim. Biophys. Acta 93, 402 (1964). Cylindrocarpon radicicola on 16a,17a-oxidoprogesterone (I) gave 20a-hydroxy-16a,17a-oxido-4-pregnen-3-one (II), 20a-hydroxy-16a,17a-oxido-l,4-pregnadien-3-one (III), 16a-hydroxy-17a-oxa-l,4-androstadiene-3,17-dione (IV) and 16a,17a-dihydroxy-l,4-androstadien-3-one (V). Sequence and mechanism of degradation are discussed. 16a-Hydroxy-4-pregnene-3,20-dione gave (V) only. 16a-Hydroxy-4-androstene-3,17-dione gave (IV) and (V).
Ap-20 El-Tayeb, O. , Knight, S. G., and Sih, C. J. , Biochim. Biophys. Acta 93, 411 (1964). 17a-Hydroxyprogesterone with Pénicillium citrinum gave 12/3-hydroxylation and 15/3-hydroxylation. Cylindrocarpon radicicola gave 17a-oxa-l,4-androstadiene-3,17-dione from either 17a-hydroxyprogesterone or 16-dehydroprogesterone.
Ap-21 Eroshin, V. K. , Med. Prom. SSSR 16, 23-25 (1962).
Ap-22 Fukushima, D. K. , J . Biol. Chem. 239, 1748 (1964). 3a-Hydroxy-5/3-androstane-17-one and 5/3-androstane-3,17-dione were hydroxylated at 7/3- by Pénicillium sp.
Ap-23 Fukushima, D. K. , and Noguchi, S. , Federation Proc. 24, 414 (1964). Andro-sterone and Pénicillium sp. gave 12/3-hydroxylation. Epiandrosterone with the same organism gave la-hydroxylation. 5a-Androstane-3,17-dione gave some l a , 3/3-dihydroxy-5a-androstan-17-one. 3/3-Hydroxy-5/3-androstan-17-one gave the 7/3-ol and 7/3-hydroxy-5/3-androstane-3,17-dione.
Ap-24 Gibian, H., Kieslich, K., Koch, H. J . , Kosmol, H. , Rufer, C . , Schröder, E . , and Vossing, R. , Tetrahedron Letters 21, 2321 (1966). Asymmetric reduction with Saccharomyces sp. and Bacillus thuringiensis of a carbonyl group in a totally synthetic, optically inactive steroid precursor.
Ap-25 Gibson, D. T . , Wang, K. C. , Sih, C. J. , and Whitlock, H. , J r . , J . Biol. Chem. 241, 551 (1966). The structures of several nonsteroidal degradation products from the action of Nocardia restrictus on A4-3-ketosteroids, and insights into the mech-anism of degradation derived therefrom; also J . Am. Chem. Soc. 87, 1386 (1965).
BIBLIOGRAPHICAL APPENDIX 723
Ap-26 Greenspan, G. , Rees , R . , Smith, L. L. , and Alburn, H. E. , J. Org. Chem. 30, 4215 (1965). 11a -Hydroxylation and 12/3-hydroxylation of steroidal alkaloids (funt-umine and funtumidine) by Aspergillus ochraceus.
Ap-27 Greenspan, G . , Smith, L. L. , Foel l , T. J . , and R e e s , R . , U .S . Patent 3 ,231 ,589 (1966). Hydroxylation of 18-homo-19-nortestosterone at lß,6ß,10/3, a n d l l a b v
Aspergillus ochraceus.
Ap-28 Greenspan, G. , Smith, L. L . , Rees , R. , Foel l , T. J . , and Alburn, H. E. , J. Org. Chem. 31 , 2512 (1966). Microbial transformation of steroids of the unnatural ( / ) s e r i e s , and simultaneous transformation of other d- and I -substrates by the same cultures.
Ap-29 Grozdyak, P. I . , Med. Prom. SSSR 16, 26-28 (1962).
Ap-30 Holmlund, C. E . , Sax, K. J. , Blank, R. H. , and Evans, R. H. , Jr . Steroids 5, 459 (1965). 7/3-Hydroxylation and deacetylation of 16a -methy l -17a , 21-dihydroxy-4-pregnene-3,20-dione 21-acetate with Rhizopus nigricans. 1 la-Hydroxylation and deacetylation of the same substrate with Dactylium dendroides.
Ap-31 Iida, M. , Townsley, J. D. , Hayano, M . , and Brodie, H. J. , Steroids, Suppl. 1, p. 159 (1965). Reversible A1-dehydrogenating-hydrogenating enzyme system i s o -lated from Bacillus cyclo-oxydans. Dependence on cofactors and enzyme induction discussed.
Ap-32 Irmscher , K. , Bier Stecher, W. , Metz, H. , Watzel, R . , and Bork, K. H. , Ber . 97, 3363 (1964). A1-Dehydrogenation of 7α-hydroxytestosterone and 7a-acetoxy-methyltestosterone by Corynebacterium simplex. 7a-Hydroxylation of methyltes-tosterone and testosterone by Curvularia lunata and Cunninghamella blakesleeana.
Ap-33 Jeruss i , R. , and Ringold, H. J. , Biochemistry £» 2113 (1965). Enzyme kinetics of 1,2-dehydrogenation using cellfree preparations of Bacillus sphaericus. Comments on mechanism.
Ap-34 Kogan, L. M . , Ulezlo, I. V . , Kozlova, I. K. , Suvorov, N.. N. , Portnova, S. L . , ^ Skryabin, G. K. , and Torgov, I. V. , Izv. Akad. Nauk SSSR, Ser. Khim. No. 11 , p. 2008-2015 (1964).
Ap-35 Kogan, L. M. , Vorshvil lo, W. E . , Skryabin, G. K. , and Torgov, I. V . , Dokl. Akad. Nauk SSSR 160, 346-348 (1965).
Ap-36 Kondo, E . , Kogyo Kagaku Zasshi 67, 724-727 (1964).
Ap-37 Kondo, E. , and Mitsugi, T . , J. Am. Chem. Soc. 88, 4737 (1966). Degradation of spiroketal side chain in diosgenin and tigogenin by Fusarium solani and Corynebac-terium simplex. Formation of l ,4-androstadiene-3 ,16-dione in 65% yield. D i s -cussion of mechanism.
Ap-38 Kondo, E . , Mitsugi, T . , and Tori, K. , J. Am. Chem. Soc. 87, 4655 (1965). 18-Hydroxylation of corticosterone by Corynespora cass i icola and Corynespora melonis . Microbial synthesis of aldosterone.
Ap-39 Kurosawa, Y. , Shimojima, H. , and Osawa, Y. , Steroids Suppl. 1, p. 185 (1965). Resolution of totally synthetic steroid precursors by yeast and pancreatic enzymes.
Ap-40 Koscheenko, K. A . , Skryabin, G. K. , Eroshin, V. K. , Kogan, L. M . , and Torgov, I. V . , Prikl . Biokhim. i Mikrobiol. 1', 127-130 (1965).
Ap-41 Kuchaeva, A. G. , and Capek, A . , Microbiology (USSR) (English Transi .) 32 , 843-846 (1964).
Ap-42 Laskin, A. I . , Fried, J. , Cohen, A. I. , Meyers , C . , Grabowich, P. , Junta, B. , Pa lmere , R. M. , and Dias s i , P. A . , Steroids 5, 57 (1965). 2/3 -Hydroxylation of
724 Vu. BIBLIOGRAPHICAL APPENDIX
deoxycorticosterone, 6α-fluoro-4-pregnene-16a , 17α, 21-triol-3,20-dione 16,17-acetonide, 16a-methyl- 17α ,21 -dihydroxy-4-pregnene-3,20-dione, and progesterone with Gnomonia fragariae. 14a-Hydroxylation and 2jS, 16a-dihydroxylation of proges-terone by the same organism.
Ap-43 Laskin, A. I . , Grabowich, P . , Meyers, C. DeL. , and Fried, J. , J . Med. Chem. 7, 406 (1964). Eburicoic acid was transformed by Glomerella fusarioides into 3,4-seco-Δ8?M (28) -eburicadien-4-ol-3,21 -dioic acid.
Ap-44 Malhotra, S. K., and Ringold, H. J. , J . Am. Chem. Soc. 87, 3228 (1965). The mechanism of action of isomerase derived from Bacillus sphaericus.
Ap-45 Mallett, G. E. , Fukuda, D. S. , andGuynes, G. J. , Abstr. 150th Meeting Am. Chem. S o c , Atlantic City, 1965, p. 12Q.
Ap-46 Manson, A. J. , Sjogren, R. E. , and Riano, M. , J . Org. Chem. 30, 307 (1965). Reduction of 17a-ethinyl-17ß-hydroxy-2-hydroxymethylene-4-androsten-3-one by Rhizopus stolonifer to the corresponding 2a-hydroxymethyl product.
Ap-47 Martinkova, J . , and Dyr. J. , Collection Czech. Chem. Commun. 30, 2994 (1965).
Ap-48 Marx, A. F . , Beck, H. C. , van der Waard, W. F. , and de Flines, J. , Steroids 8, 421 (1966). Incubation of concessine with atachybotrys parvispora gave Δ4 -conenin-3-one and lla-hydroxy-Δ4 -conenin-3-one. Fermentation with Gloeo-sporium fructigenum gave 7a-hydroxyconessine, 7/3-hydroxyconessine, and 11a-hydroxyconessine.
Ap-49 Marx, A. F. , Beck, H. C. , van der Waard, W. F. , and de Flines, J . , Steroids 8_, 391 (1966). 9a-Hydroxylation and 12a-hydroxylation of conessine with Botryodi-plodia theobromae.
Ap-50 Modelli, R. , Ann. Chim. (Rome) 55, 205 (1965). 16a-Hydroxylation of 17a-methyltestosterone and 4-hydroxy-17a-methyltestosterone by Nocardia italica.
Ap-51 Modelli, R. , Ann. Chim. (Rome) 55, 310 (1965). 2a-Hydroxylation and 16a-hydroxylation of 4-estrene-3,17-dione and 19-nortestosterone by Nocardia italica.
Ap-52 Neidleman, S. L. , Diassi, P. A. , Junta, B. , Palmere, R. M. , and Pan, S. C. , Tetrahedron Letters, p. 5337 (1966). 17a-Chlorination and 17a-bromination of 16-ketoprogesterone and 16 -keto - A- nor -progesterone by enzymes from Caldario-myces f urn ago together with hydrogen peroxide and a source of halide ion. 16,16-Dibromination of 15-keto-1-denydrotestololactone under same conditions. Proofs of structure by comparison with samples prepared by nonenzymatic halogenation. No enzymatic halogenation occurred with substrates lacking the /3-dicarbonyl structural element. Also 15a-hydroxylation of 1-dehydrotestoloactone by Pénicillium sp. Work by Brown and Hager [J. Am. Chem. Soc. 89, 719 (1967)] indicates that the enzymatic reaction involves generation of Cl from Cl~ and hydrogen peroxide. The inference may be drawn that there is no steroid-enzyme interaction required in the halogenation examples shown by Neidleman.
Ap-53 Noda Institute for Scientific Research, Netherlands Patent 6,502,883 (1965) (Japanese Patent 30915 (1964); Derwent Abstr. 19, 293). Degradation of choles-terol, sitosterol, or stigmasterol by Corynebacterium simplex and other known 1-dehydrogenating species, in the presence of agents which chelate copper or iron, to give 4-androstene 3,17-dione, 1,4-androstadie ne-3,17-dione, and other products.
Ap-54 Noguchi, S. , and Fukushima, D. K. , J . Org. Chem. 30, 3552 (1965). Pénicillium sp. with 3a-hydroxy-5a-androstan-17-one gave 12j3-hydroxy product. The same organism with 3j3-hydroxy-5a-androstan-17-one gave the Ια-hydroxy product and with 3j3-hydroxy-5j3-androstan-17-one gave the 7j3-hydroxy product and 7/3-hydroxy-5j3-androstane-3,17-dione.
BIBLIOGRAPHICAL APPENDIX 725
Ap-55 Okada, M. , and Hasunuma, M., J. Pharm. Soc. Japan 86̂ , 67 (1966). 7ß-Hydroxy-lation of digitoxigenin with Cunninghamella blakesleeana.
Ap-56 Okada, M. , Hasunuma, M. , and Saito, Y. , J . Pharm. Soc. Japan 85, 1092 (1965). 12/3-Hydroxylation of bufalin and resibufogenin with Gibberella saubinetti.
Ap-57 Okada, M. , and Saito, Y. , Steroids £, 651 (1965). Assignment of structure to Ία., 15a-dihydroxylated product from Gibberella saubinetti on dehydroepiandrosterone.
Ap-58 Okada, M. , Yamada, A. , and Ishidate, J . Pharm. Soc. Japan 85, 816 (1965). 7a -Hydroxylation of dehydroepiandrosterone with Gibberella saubinetti. 15a-Hydroxy-lation of progesterone, deoxycorticosterone, and testosterone with the same organism.
Ap-59 Okumura, T . , Nozaki, Y. , and Satoh, D. , Chem. & Pharm. Bull. (Tokyo) 12, 1143 (1964). 3/3, 14jS, 21-Trihydroxy-5/3-pregnan-20-one gave 1/3-hydroxylation with Absidia orchidis. From 4,5-dehydrodigitoxigenone the 7/3-hydroxy and 7/3,12/3-dihydroxy products were characterized.
Ap-60 Peterson, G. E. , and Davis, J. R. , Steroids 4, 677 (1964). Degradation of cho-lesterol by Streptomyces sp.
Ap-61 Prochazka, Z . , and Sorm, F . , Collection Czech. Chem. Commun. 30, 1874 (1965). l i a -Hydroxylation of 14/3,18-cycloprogesterone (10j3-methyl-13/3,14/3-cyclomethy-lene-17/3-acetyl-4-gonen-3-one) with Rhizopus nigricans.
Ap-62 Prouva, J. , Schwartz, V. , and Syhora, K. , Folia Mikrobiol. (Prague) 9, 218-221 (1964).
Ap-63 Rahim, M. A. , and Sih, C. J . , J . Biol. Chem. 241, 3615 (1966). In vitro studies of oxygenase and esterase from Cylindrocarpon radicicola. Degradation of proges-terone , 17a? -hydroxyprogesterone, 16-dehydroprogesterone, deoxycorticosterone, and 16a , 17a-oxidoprogesterone to C-19 steroids.
Ap-64 Raman, P. B. , and Per on, F. G., Steroids 5, 249 (1965). 11/3-Hydroxylation of 18,21-dihydroxy-4-pregnene-3,20-dione with Cunninghamella blakesleeana.
Ap-65 Reimann, H. , Sarre, O. Z. , and Oliveto, E. P . , Steroids 7_, 505 (1966). Con-version of a 3/3-hydroxy-Δ5 -steroid to a 3-keto-Δ4 -steroid with Flavobacterium dehydrogenans.
Ap-66 Sato, Y. , Waters, J. A. , and Kaneko, H. , J . Org. Chem. 29, 3732 (1964). 9a -Hydroxylation and 7/3-hydroxylation of 5,6-dihydrosolasodine by Helicosytum pir i -forme.
Ap-67 Saucy, G., Eis, H. , Miksch, F . , and Fürst , A. , Helv. Chim. Acta 49, 1529 (1966). lia-Hydroxylation of 9/3,10α -substrates ("retrosteroids") by Aspergillus ochraceus.
Ap-68 Sax, K. J . , Holmlund, C. E. , Feldman, L. I. , Evans, R. H. , J r . , Blank, R. H. , Shay, A. J . , Schultz, J . S. , and Dann, M., Steroids 5, 345 (1965). I a , 2 a - D i -hydroxylation of 17a-ethynyl-17/3-hydroxy-4-androsten-3-one, 9a-fluoro-ll/3,17/3-dihydroxy-17a-methyl-4-androsten-3-one, and ll/3,21-dihydroxy-16a ,17a-isopro-pylidenedioxy-4-pregnene-3,20-dione by inducible enzyme from Nocardia corallina. Same reaction with a Δ1 -substrate, proposed as intermediate in this process.
Ap-69 Schubert, K., Böhme, K. H. , and Hörhold, C. , Z. Naturforsch. 18b, 988 (1963). Degradation of deoxycorticosterone acetate by Mycobacterium smegmatis. Isolation of fragment with only C and D rings from original skeleton intact.
Ap-70 Schubert, K., Groh, H. , and Ho'rhold, C. , Naturwiss. 52, 20 (1965). Degradation of cholesterol and 4-cholesten-3-one by Mycobacterium smegmatis to 9,10-seco-Δ ι, 3,5 do >_andr ostatr ien-3 -ol -9,17 -dione.
VII. BIBLIOGRAPHICAL APPENDIX
Ap-71 Schubert, K. , Schlegel, J . , and Ho'rhold, C., Steroids, Suppl. 1, p. 175 (1965). Clostridium paraputrificum reduces 3-keto-Δ4-steroids to 3a?-hydroxy-4,5ß-di-hydrosteroids; 3-keto-Δ1*4 -steroids to 3-keto-A1 -4,5/3-dihydrosteroids and 3αι-hydroxy-l,2,4,5/3-tetrahydrosteroids; 3-keto-Δ4»6-steroids into Δ6 -3a-hydroxy-4,5/3-dihydrosteroids; and 3-keto-AM?6-steroids to Δ6-3o?-hydroxy-1,2,4,5/3-tetr ahy drosteroids.
Ap-72 Schubert, A. , and Schwarz, S., Experientia 21, 562 (1965). Dehydrogenation at 1- with Mycobacterium sp. and lla-hydroxylation with Rhizopus nigricans using several unusual twenty-carbon substrates.
Ap-73 Schupbach, M. , and Tamm, C. , Helv. Chim. Acta 47, 2217 (1964). Incubation of 14ß,15ß-epoxy-14-anhydro-digitoxigenin with Fusarium lini gave the 12j3-hydroxy product. The same organism with resibufogenin also gave 12/3-hydroxy product.
Ap-74 Schupbach, M. , and Tamm, C. , Helv. Chim. Acta 47, 2226 (1964). Marinobu-fagenin with Fusarium lini gave the 12/3-hydroxy product.
Ap-75 Schuytema, E. C. , Hargie, M. P. , Merits, I. , Schenck, J . R. , Siehr, D. J . , Smith, M. S. , and Varner, E. L. , Biotechnol. Bioeng. 8, 275 (1966). Use of basidiomycetes to hydroxylate (6β, 11α, 17α), reduce (5a-H), and degrade (17/3-Ac —♦ 17a-oxa-17-ketone) progesterone.
Ap-76 Schwarz, V. , Ulrich, M. , and Sy hor a, K. , Steroids 4, 645 (1964). Production of the 1/3-hydroxy product, along with cortisol and 11-epicortisol, by Absidia orchidis on Compound S.
Ap-77 Shaw, D. A., Borkenhagen, L. F . , and Talalay, P . , Proc. Natl. Acad. Sei. U.S. 54, 837 (1965). Identification of amino acids into which fragments of androstene-dione, formed by degradation with Pseudomonas testosteroni, are incorporated.
Ap-78 Shirasaka, M. , Sankyo Kenyusho Nempo 15, 1-35 (1963).
Ap-79 Sih, C. J. , Lee, S. S. , Tsong, Y. Y. , and Wang, K. C. , J . Am. Chem. Soc. 87, 1385 (1965). Nocardia restrictus on 6/3,19-oxido-4-androstene-3,17-dione gave the 9a -hydroxy product. 9a , 19-Dihydroxy-4-androstene-3,17-dione gave 3,19-di-hydroxy-9,10-seco-l, 3,5(10) -androstatriene-9,17-dione. 2,17/3-Dihydroxy-l,4-androstadien-3-one gave 2£,9a-dihydroxy-4-androsten-3,17-dione. 2-Methoxy-17/3-hydroxy-1,4-androstadien-3-one gave 2-methoxy-3,4-dihydroxy-9,10-seco-l,3,5(10)-androstatrien-9,17-dione. 4,9a,17/3-Trihydroxy-4-androsten-3-one gave 3,4-dihydroxy-9,10-seco-l,3,5(10)-androstatriene-9,17-dione which in turn could be degraded further by N. restrictus. Comments on mechanism of degradation.
Ap-80 Sih, C. J. , Lee, S. S. , Tsong, Y. Y. , and Wang, K. C. , J . Biol. Chem. 241, 540 (1966). Degradation mechanisms with Nocardia restrictus.
Ap-81 Sih, C. J. , Lee, S. S. , Tsong, Y. Y. , Wang, K. C. , and Chang, F. N. , J . Am. Chem. Soc. 87, 2765 (1965). 6j3,19-Oxido-4-cholesten-3-one with Nocardia restrictus gave 6/3,19-oxido-4-androsten-3,17-dione ( I ) . 3/3-Acetoxy-5-cholesten-19-ol with organism CSD-10 gave estrone in 72% yield. 3/3-Acetoxy-5a-chloro-6/3,19-oxidocholestane with CSD-10 gave ( I ) .
Ap-82 Sih, C. J . , Lee, S. S. , Wang, K. C . , and Tsong, Y. Y. , Bacteriol. Proc. p. 93 (1965). Mechanism of A-ring degradation by Nocardia restrictus. See also Ap-79.
Ap-83 Sih, C. J . , and Wang, K. C. , J. Am. Chem. Soc. 87, 1387 (1965). 19-Hydroxy-4-cholesten-3-one with Nocardia restrictus gave estrone. 19-Hydroxy-/3-sitost-4-en-3-one gave estrone.
Ap-84 Singh, K., Sehgal, S. N. , and Vezina, C. , Can. J . Microbiol. 11, 351 (1965). Detailed study of the influence of medium and other environmental conditions on the 1-dehydrogenation of Compound S by spores of Septomyxa affinis. Evidence that
726
BIBLIOGRAPHICAL APPENDIX 727
the required enzyme is constitutive and not induced. Mention of a variety of other spore-forming organisms, spores from which Δ1 -dehydrogenate Compound S.
Ap-85 Skryabin, G. K. , Zryagintseva, I. S. , and Sokolova, L. V. , Izv. Akad. Nauk SSSR, Ser. Biol. 29, 715-20 (1964).
Ap-86 Smith, L. L. , Greenspan, G. , Rees, R. , and Foell, T . , J . Am. Chem. Soc. 88, 3120 (1966). Aspergillus ochraceus on racemic 19-nortestosterone gave Z-l/3-hy-droxy, d-6/3-hydroxy, Z-10j3-hydroxy, and d-l la-hydroxy products. Similar, but not identical, results with racemic higher 18-homologs.
Ap-87 Sokolova, L. V. , Grinyuk, T. I. , Yaroslavtseva, Z. A. , Kovylkina, N. F. , Gusa-kova, E. G. , Skryabin, G. K. , and Suvorov, N. N. , Med. Prom. SSSR 16, 26-28 (1962).
Ap-88 Suvorov, N. N. , Novikova, V. M., Sokolova, L. V. , and Kovylkina, N. F . , Med. Prom. SSSR 14, 22-24 (1960).
Ap-89 Talalay, P . , and Boy er , J . , Biochim. Biophys. Acta 105, 389 (1965). Preparation of crystalline Δ 5 -isomerase from Pseudomonas testosteroni on a large scale.
Ap-90 , Tori, K., and Kondo, E. , Steroids 4, 713 (1964). NMR method for determination of position of hydroxyl group introduced by microbiological transformation. 15a-Hydroxylation from Helminthosporium sigmoideum on Compound S. 15/3-Hydroxy-lation from Cercospora melonis on Compound S. 7 α, 14α -Dihydroxylation from Curvularia lunata on Compound S. 6/3,llo?-Dihydroxylation by Cunninghamella echinulata on progesterone.
Ap-91 Tsong, Y. Y. , Wang, K. C. , and Sih, C. J . , Biochim. Biophys. Acta 93, 398 (1964). Reduction of Δ6 in 17ß-hydroxy-4,6-androstadien-3-one by Nocardia r e -strictus. Other products include 9a-hydroxy-4,6-androstadien-3,17-dione and 9a , 17/3-dihydroxy-4,6-androstadien-3-one.
Ap-92 van der Sijde, D., de Flines, J . , and van der Waard, W. F . , Rec. Trav. Chim. 85, 721 (1966). Fermentation of 17a,21-dihydroxy-9/3,10a-pregn-4-ene-3,20-dione with Aspergillus ochraceus yielded 11a, 17a,21-trihydroxy-9/3,10a-pregn-4-ene-3,20-dione and 15a,17a,21-trihydroxy-9/3,10a-pregn-4-ene-3,20-dione. Fermen-tation of 9/3,10α -progesterone with Aspergillus ochraceus afforded 11a-hydroxy-9ß, 10a -progesterone. Fermentation of the latter product with Sporomia pollaccii and Helicosporium lumbricopsis afforded 1 l a -hydroxy-9/3,10a -testosterone and 11a-hydroxy-9/3,10a-androst-4-ene-3,17-dione. Fermentation of 9β, 10α-testos-terone with Aspergillus ochraceus yielded 1 l a -hydroxy-9)3,10a -testosterone and 11a -hydroxy-9ß, 10a -androst-4-ene-3,17-dione. Fermentation of 17a -hydroxy-9/3,10a-progesterone with Aspergillus ochraceus afforded l la,17a-dihydroxy-9/3,10a-progesterone and 11a-hydroxy-9/3,10a-androst-4-ene-3,17-dione.
Ap-93 van der Waard, W. F . , van der Sijde, D., and de Flines, J . , Rec. Trav. Chim. 85, 712 (1966). Fermentation of progesterone, 9β, 10α-progesterone, 6-dehydro-9/3, 10a-progesterone, and 9/3,10a-testosterone with Sepedonium ampullosporum af-forded the respective 16a-hydroxy derivatives.
Ap-94 Wacker, A. , Drews, J. Pratt , W. B. , Lawrent, H. , and Petzoldt, K. , Z. Natur-forsch. 20b, 547 (1965). Study of steroid-initiated enzyme induction in Pseudo-monas testosteroni with respect to kinetics, strengths of various inducers, and other factors.
Ap-95 Wang, K. C. , Lee, S. S. , Tsong, Y. Y. , Sih, C. J . , Abstr. 150th Meeting Am. Chem. Soc., Atlantic City, 1965, p. 13Q. Failure of Nocardia and Mycobacteria sp. to convert l,3,5(10)-cholestatrien-3-ol into estrone.
Ap-96 Wiechert, R. , Kerb, U. , and Kies lieh, K. , Ber. 96, 2765 (1963). 11/3-Hydroxy-lation of l a -methyl Compound S with Çurvularia lunata.
728 VII. BIBLIOGRAPHICAL APPENDIX
Ap-97 Wiecher t , R. , Z. Naturforsch. 19b, 944 (1964). 1 Iß-Hydroxy 1 ation of la -me thy l -t e s tos te rone and l a -methyl Compound S with Curvu la r i a lunata.
Ap-98 Wilson, J . , and Vest l ing, C. S. , Arch . Biochem. Biophys. 110, 401 (1965). P r e p -ara t ion of a cel l f ree 15a-hydroxyla t ing sys tem from Bacil lus mega te r ium.
Ap-99 Zakrzewski , Z. , Raczkowska, S . , and Lewenstein, W. , P r z e m y s l . Chem. 4 3 , 564-565 (1964).
Ap-100 Zvyagintseva, I. S. , and Skryabin, G. K . , Izv. Akad. Nauk SSSR, Ser . Biol . 24, 525-532 (1964).