Second Supplements. to the 2nd Edition of

RODD'S CHEMISTRY OF

CARBON COMPOUNDS

A modern comprehensive treatis e

Edited byMALCOLM SAINSBURY

School of Chemistry, The University of Bath ,Claverton Down, Bath BA2 7AY, England

Second Supplement to

VOLUME II ALICYCLIC COMPOUNDS

Part A: Monocarbocyclic Compounds to and includin gFive Ring Atoms

Part B : Six- and Higher-membered MonocarbocyclicCompounds (Partial: Chapter 5 in this volume)

Alicyclic Compounds ; Monocarbocyclic Compounds to and including Five Ring Atom s

Six- and Higher-membered Monocarbocyclic Compounds (Partial )

Preface i xList of common abbreviations and symbols used xvi i

Chapter 1 . Alicyclic Hydrocarbons, Conformation and Stereochemistryby TA . CRABS and A.V. PATE L

1 . Introduction 12 . Three-membered rings 2

(a) Cyclopropanes with unsaturated substituents 2(b) Cyclopropanes with saturated substituents 6

3 . Four-membered rings 8(a) Cyclobutanes 8(b) Monosubstituted cyclobutanes 9(c) Disubstituted cyclobutanes 1 1(d) Unsaturated four-membered ring carbocycles 1 2(e) Cyclobutanones 1 2

4 . Five-membered rings 1 3(a) Cyclopentane 1 3(b) Cyclopentene 1 4(c) Cyclopentanone 1 4

5. Six-membered rings 1 5(a) Cyclohexane 1 5(b) Monosubstituted cyclohexanes 1 6

(i) A-value determination on hydrogen isotopes and alkyl groups, 17 -(ii) A-value determinations on substituents other than alkyl, 18 -

(c) 1,1-Disubstituted cyclohexanes 2 0(d) 1,2-Disubstituted cyclohexanes

2 4(i) Interactions involving alkyl groups, 24 - (ii) Interactions involvingelectronegative substituents, 25 -

(e) 1,1,2-Trisubstituted cyclohexanes 2 9(f) 1,3- and 1,3,5-Substituted cyclohexanes 3 2(g) 1,4-Disubstituted cyclohexanes 3 3(h) Sterically crowded cyclohexanes 3 4(i) Cyclohexene 3 6(j) 1,3-Cyclohexadiene 4 1(k) 1,4-Cyclohexadienes 4 2(1) Exomethylenecyclohexane

4 5(i) 2-Substituted exomethylenecyclohexanes, 45 - (ii) 3-Substituted exo-methylenecyclohexanes, 47 -

(m)Cyclohexanones, cyclohexanediones and cyclohexenones 49

6 . Seven-membered rings 5 4(a) Cycloheptanes 5 4(b) Cycloheptanones 5 6(c) Cycloheptene and cycloheptene oxide 57(d) Cycloheptadienes and cycloheptatrienes 5 9

7 . Eight-membered rings 6 0(a) Cyclooctanes 6 0(b) Cyclooctanones 6 2(c) Cyclooctene, cyclooctyne and 1,2-cyclooctadiene 6 3(d) 1,3-, 1,4- and 1,5-cyclooctadienes 64(e) Cyclooctatrienes 68

8 . Nine-membered rings 6 9(a) Cyclononane, cyclononanone and cyclononyne 6 9(b) 1,2-Cyclononadiene and 1,5-cyclononadiene 70(c) Cyclononatrienes 7 1

9 . Ten-membered rings 7 210 . Ring systems larger than ten-membered 74

Chapter 2. The Cyclopropanesby H .N .C . WON G

1 . Introduction 8 12 . Preparation of cyclopropanes 8 2

(a) Intramolecular nucleophilic substitution 8 2(b) Simmons-Smith reaction 8 4(c) Reaction of alkenes with diazo compounds 8 7(d) Reaction of alkenes with dihalocarbenes and other carbenoids 9 0(e) Ring contraction of cyclobutanes 9 3(f) Reactions of electron deficient carbon-carbon double bonds with phospho -

ranes, sulfuranes and arsenic ylides 9 4(g) Photochemical reaction 9 8(h) Radical mediated reaction 10 0(i) Organometallic reaction 10 1(j) Miscellaneous reaction 10 2

3 . Use of cyclopropanes in organic synthesis 10 3(a) Thermal ring fission

10 4(i) Cyclopropylidene-allene rearrangement, 104 - (ii) Cyclopropylmethylcarbene rearrangement, 105 - (iii) Vinylcyclopropane-cyclopentene rear-rangement, 106 - (iv) Divinylcyclopropane-cyclohepta-1,4-diene rearrange-ment, 108 - (v) Miscellaneous thermal fission, 109 -

(b) Reductive and oxidative ring fission

11 0(i) Reductive ring fission, 110 - (ii) Oxidative ring fission, 112 -

(c) Electrophilic and nucleophilic ring fission

11 3(i) Electrophilic addition, 113 - (ii) Retro-aldol type reaction, 114 -(iii) Cyclopropylcarbinyl cation rearrangement, 116 - (iv) Imine-cyclo-propane and carbonyl-cyclopropane rearrangements, 118 - (v) Nucleophili caddition, 119 -

(d) Radical mediated ring fission

12 1(i) Fission of cyclopropane by radical, 121 - (ii) Cyclopropylcarbinyl radica lrearrangement, 12] -

(e) Metal salt mediated ring fission 122

Chapter 3. The Cyclobutanesby D .T. HURS T

1 . Introduction, structure, properties, and theoretical considerations 12 52. Synthesis of the cyclobutane ring system 12 9

(a) [2+2] Cycloaddition reactions 12 9(b) Intramolecular cyclisations 14 2(c) Ring expansion reactions 14 6(d) Ring contractions 14 8

3. Reactions of cyclobutanes 15 0(a) Solvolyses and rearrangements of cyclobutanes and cyclobutenes 15 0(b) Electrocyclic ring opening-ring closing reactions 15 4(c) Miscellaneous reactions of cyclobutanes and cyclobutenes 15 6(d) Reactions of cyclobutanols, cyclobutanones and cyclobutenones 16 0(e) Reactions of cyclobutenenitriles 16 7(f) Reactions of squaric and semisquaric acids 16 8

Chapter 4a. The Cyclopentanesby D.T. HURS T

1 . Reviews, theoretical and structural aspects, general properties 1732. Synthesis 175

(a) Cyclisation reactions leading to cyclopentanes, cyclopentenes ; general cyclo -pentane ring synthesis 175

(b) Cyclopentanes and cyclopentenes by cycloaddition reactions 182(c) Cyclopentanes and cyclopentenes by ring expansion and ring contraction

processes(d) Cyclopentanones and cyclopentenones by cyclisation processes 189(e) Cyclopentanones and cyclopentenones by cycloaddition reactions 200(f) Cyclopentanones and cyclopentenones by ring expansion and ring contrac-

tion reactions 203(g) Cyclopentanones and cyclopentenones by rearrangements and by niiscella -

neousreactions 2053 . Reactions

(a) Cyclopentanes, cyclopentenes, and simple derivatives 209(b) Cyclopentanones, cyclopentenones, and derivatives 21 2

Chapter 4b. Natural Products Containing the Cyclopentane Sub-unit :Prostaglandins

by R .J K. TAYLOR, S .G PYKE and S .M PYKE

1 . Introduction 22 12 . Structure and nomenclature 22 33 . Prostaglandin biosynthesis 23 0

(a) Mammalian biosynthesis 23 0(b) Non-mammalian biosynthesis 23 8

4 . Prostaglandin total synthesis 24 3(a) Corey's bicyclic lactone approach 24 4(b) Approaches uia polycyclic intermediates 24 9(c) Conjugate addition and three component coupling approaches 25 2(d) Recent synthetic approaches to PGs 25 9(e) PG metabolism and analogue synthesis 263

(f) Synthesis of non-mammalian prostanoids 26 75 . Bibliography - . - 27 6

(a) General and biological 27 6(b)Synthetic 27 9

Chapter 4c . Cyclopenladien eby D.F EWIN G

1 . introduction 28 32. Preparation of rr-bonded cyclopentadiene derivatives 28 3

(a) Deuteriated cyclopentadiene 28 3(b) Alkyl substituents

28 4(i) Therinolysis, 284 - (ii) Alkylation, 284 - (iii) From fulvenes, 288 -(iv) Cyclisation, 289 -

(c) Cyano, carbonyl, carboxyl and tritluoromethyl substituents 29 1(d) Phosphine substituents 29 2(e) Other substituents 29 3

3. Ionic metal derivatives 29 44 . Fluxionality of cyclopentadienyl derivatives 29 65. Metal complexes - structure and reactions 29 7

(a) The cyclopentadienyl Iigand

29 7(i) Bonding, 298 - (iii Effect of substituents in the cyclopentadieny lring, 300 -

(b) Monoligating cyclopentadienyl complexes 30 4(i) Complexes of main group metals, 304 - (ii) Transition group metallo -cenes, 305 - (iii) Cluster complexes, 309 - (iv) Other complexes, 310 -(v) Lanthanides and actinides, 313 -

(c) Bridged biscyclopentadiene complexes

31 4(i) Metallocenophanes, 314 - (ii) Bridged binuclear complexes, 319 -

(d ) Bifunctional cyclopentadienyl ligands 32 56. Metal complexes - applications

32 7(i) Catalysts and chiral auxiliaries, 327 - (ii) Biochemistry, 329 - (iii) Liqui dcrystals, 329 -

7 . Reactions of cyclopentadiene 33 0

Chapter 5a . Cyclohexane and its Derivativesby It. BOLTO N

Introduction 33 51. Cyclohexane 33 6

(a) Synthesis

33 6(i) From benzene, 336 - (ii) From cyciohexene, 339 - (iii) By cracking pro-cesses, 391 -

2. Halogenocyclohexanes 34 2(a) Fluoroeyclohexsnze and derivatives

34 2(i) Synthesis, 342 - (ii) Reactions, 34G -

(b) Chlorocyclohexane

34 7(i) Synthesis, 347 - (ii) Reactions, 349 -

(c) Bromocyclohexane

35 0(i) Reactions of bromocyclohexane, 351 -

(d) Halogenocyclohexanes through addition to benzene rings 353

3 . Cyclohexadienyl intermediates 35 6(a) Cyclohexadienyl radical 35 7(b) Muonium attack 35 9(c) Cyclohexadienylium ion

35 9(i) Attack at a substituted benzene carbon atom, 360 - (ii) Generation ofstabilised cyclohexadienylium ions, 361 -

4 . Cyclohexanol and cyclohexanone 36 2(a) Synthesis

36 2(i) From phenol and phenol ethers, 362 - (ii) From cyclohexane, 364 -(iii) From cyclohexene, 367 -

Cyclohexadienones and derivatives 36 8(a) Identification and preparation 36 8

6 . Cyclohexanamine (cyclohexylamine) 37 2

Chapter 5b. Natural Products Containing a Cyclohexane, Cyclohexene, orCyclohexadiene Subuni t

by G .W. GRIBBLE

1 . Simple examples 37 5(a) Nonfunctionalized 37 5(b) Functionalized

37 7(i) Amino acids, 377 - (ii) Oxygenated cyclohexanes, 377 - (iii) Oxygenatedcyclohexenes, 379 -

2 . Nonfunctionalized or unusual terpenoids 38 1(a) Monoterpenoids 38 1(b) Nonfunctionalized sesquiterpenes 38 1(c) Norsesquiterpenes 38 2(d) Furanoterpenes 38 3(e) Oxygenated norterpenoids 38 4(f) Rearranged or unusual terpenoids 38 5

3 . C13 Norterpenoids 38 84 . Flavonoid, chalcone, and coumarin types 39 65 . Shikimic acid pathway 39 8

(a) Mechanistic aspects

40 0(i) Step 1, 400 - (ii) Step 2, 401- (iii) Step 3, 401 - (iv) Step 5, 402 - (v) Step6, 402 - (vi) Step 7, 403 - (vii) Step 8, 404 -

(b) Synthesis

40 4(i) Natural metabolites and derivatives, 404 - (ii) Analogues, 405 -

(c) Natural occurrence 40 66 . Cyclitols 40 7

(a) Natural occurrence 40 8(b) Synthesis 41 2(c) Cyclitol epoxides

41 4(i) Natural occurrence, 414 - (ii) Biogenesis, 416 - (iii) Synthesis, 418 -

7 . Inositols 41 9(a) Natural occurrence 42 0(b) Synthesis

42 1(i) myo-Inositols, 421 - (ii) myo-Inositol analogues, 423 - (iii) myo-Inosito lphosphates, 424 - (iv) myo-Inositol phosphate analogues, 426 - (v) Otherinositols, 429 -

8 . Pseudosugars

43 0(a) Natural occurrence 43 0(b) Synthesis 43 1

9 . Aminocyclitols 43 2(a) Natural occurrence 43 2(b) Synthesis 43 7

10 . Benzoquinones 43 911 . Quinols 44 112 . Halogenated tyrosine metabolites 44 313 . Concluding remarks 44 5

Chapter 5c . Cyclohexadienesby A.J. PEARSO N

1 . Introduction 44 72 . Preparation of cyclohexadienes 44 7

(a) Metal-ammonia (Birch) reduction of aromatic compounds 44 7(b) Microbial oxidation of aromatic compounds 44 9(c) Cyclohexadienes from cyciohexenones 45 0

3 . Reactions of cyclohexadienes 45 1(a) Conjugation of 1,4-cyclohexadienes 45 1(b) Cycloaddition reactions 45 2(c) Palladium-catalyzed 1,4-difunctionalization 45 3

4 . Metal complexes of cyclohexadienes 45 5(a) Cyclohexadiene-Fe(CO)2 L complexes

45 5(i) Preparation, 455 - (ii) Reactions with electrophiles, 462 - (iii) Reaction swith nucleophiles, 463 - (iv) Coupling reactions with alkenes, 464 - (v) Use sof tricarbonyliron as a cyclohexadiene protecting group, 467 - (vi) De-complexation of cyclohexadiene-Fe(CO )3 complexes, 469 - (viii Conversionof cyclohexadieneiron complexes to cyclohexadienyliron cations, 470 -(viii) Reactions of cyclohexadienyliron cations, 473 -

(b) Cyclohexadiene-CoCp complexes and the derived cyclohexadienyl-CoC pcations 47 9

(c) Cyclohexadiene-Mo(CO) 2 Cp and related complexes 48 1

Guide to the Index 48 7Index 489