ORGANIC SYNTHESES BY OXIDATION WITH METAL COMPOUNDS

ORGANIC SYNTHESES BY OXIDATION WITH METAL COMPOUNDS

Edited by

w. l. MIJS

and

C. R. H. I. DE lONGE Akzo Research Corporate Research Department Arnhem. The Netherlands

PLENUM PRESS • NEW YORK AND LONDON

Library of Congress Cataloging in Publication Data

Organic syntheses by oxidation with metal compounds.

Includes bibliographies and index. 1. Chemistry, Organic-Synthesis. 2. Oxidation. 3. Organometallic compounds. 1.

Mijs, W.J. II. Jonge, Comelis R. H. I. de, 1940-QD262.07246 1986 547'.2 86-5072 ISBN-13: 978-1-4612-9248-7 e-ISBN-13: 978-1-4613-2109-5 DOl: 10.1007/978-\-4613-2109-5

© 1986 Plenum Press, New York Softcover reprint of the hardcover I st edition 1986 A Division of Plenum Publishing Corporation 233 Spring Street, New York, N.Y. 10013

All rights reserved

No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher

CONTRIBUTORS

Zivorad CekoviC • Department of Chemistry, Faculty of Science. University of Belgrade. and Institute of Chemistry, Technology, and Metallurgy, YU-llOOI Belgrade, Yugoslavia

John L. Courtney • School of Chemistry, The University of New South Wales, Kensington, NSW 2033, Australia

Suzanne F. Davison • Department of Chemistry, The University of Sheffield, Sheffield S3 7HF, England

Alexander J. Fatiadi • Organic Analytical Research Division, Center for Analytical Chemistry, National Bureau of Standards, Gaithersburg, Maryland 20899

Marcel Fetizon • Laboratoire de Synthese Organique. Ecole Poly technique, 91128 Palaiseau, Cedex. France

Fillmore Freeman • Department of Chemistry, University of California, Irvine, California 92717

M. V. George • Department of Chemistry, Indian Institute of Technology, Kanpur 208016, India

Michel Golfier • Laboratoire de Synthese Organique, Ecole Poly technique, 91128 Palaiseau, Cede x, France

Tse-Lok Ho • SCM Corporation, Organic Chemicals Division, Jacksonville, Florida 32201

C. R. H. I. de Jonge • Akzo Research, Corporate Research Department, 6800 AB Arnhem, The Netherlands

Jonathan Peter Kitchin • Minnesota 3M Research Limited, Pinnacles, Harlow, Essex CM19 5AE, England

W. J. de Klein • Akzo Research, Corporate Research Department, 6800 AB Arnhem, The Netherlands

Ljubinka Lorenc Department of Chemistry, Faculty of Science, University of Belgrade. and Institute of Chemistry. Technology, and Metallurgy, YU-11001 Belgrade, Yugoslavia

Jean-Marie Louis • Laboratoire de Synthese Organique, Ecole Poly technique, 91128 Palaiseau. Cede x, France

Peter M. Maitlis • Department of Chemistry, The University of Sheffield. Sheffield S3 7HF, England

Alexander McKillop • School of Chemical Sciences. University of East Anglia. Norwich NR4 7T1. England

Mihailo Lj. Mihailovii: • Department of Chemistry, Faculty of Science. University of Belgrade. and Institute of Chemistry, Technology, and Metallurgy, YU-11001 Belgrade. Yugoslavia

v

VI CONTRIBUTORS

Philippe Mourgues • Laboratoire de Synthese Organique. Ecole Poly technique, 91128 Palaiseau. Cedex. France

Yoshiro Ogata • Emeritus Professor of Applied Chemistry, Nagoya University, Chikusa, Nagoya, Japan

Yasuhiko Sawaki • Department of Applied Chemistry, Faculty of Engineering, Nagoya University, Chikusa, Nagoya, Japan

Hari Shankar Singh • Department of Chemistry, University of Allahabad, Allahabad 211002, India

Edward C. Taylor • Depanment of Chemistry, Princeton University, Princeton, New Jersey 08544

PREFACE

This book is concerned with the synthetic aspects of oxidation reactions involving metal compounds. which are readily available or easy to prepare. The sequence followed in the chapters is as follows: a general introduction. a limited treatment of reaction mechanisms to serve as a basis for synthesis. and scope and limitations of the oxidant system. mostly in terms of substrate and product classes. Finally, at the end of each chapter. representative synthetic procedures are given together with relevant experimental considerations.

A general table is included as an appendix. This contains substrate classes and resulting product classes, referring to the oxidative procedures in the chapters. The table provides the synthetic organic chemist with a quick overview of oxidation possibilities with metal-contain­ing oxidants, enabling him to select the right method for his purpose.

The editors hope that not only organic research chemists in industry and at universities, but also advanced undergraduate and graduate students in organic chemistry, will find this book a useful guide in the design, understanding, and practical performance of oxidative organic syntheses.

The editors are grateful to the authors not only for their contributions. containing interesting new developments in oxidation chemistry, but also for the way they fitted the text into the general framework given for the book. Their suggestions and comments are gratefully acknowledged. Thanks are also due to Mrs. A. I. Rohnstrom-Ouwejan, secretary to the editors, for her administrative support.

W.1. Mijs and C. R. H. I. de Jonge Arnhem. The Netherlands

vii

CONTENTS

CHAPTER 1. OXIDATION BY VANADIUM COMPOUNDS

Fillmore Freeman

I. Introduction ............................................................ I 2. Mechanisms ............................................................ 2

2.1. Alkanes. Alkylaromatics. and Aromatic Compounds ..................... 2 2.2. Carbon-Carbon Double Bonds: Synthesis of Epoxides and Glycols ......... 2 2.3. Hydroxy Compounds .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

2.3.1. Alcohols .................................................... 6 2.3.2. Phenols and Hydroquinones ................................... 8

2.4. Carbonyl Compounds: Ketones and Quinones .......................... II 2.5. Nitrogen Compounds ............................................... 12 2.6. Sulfur Compounds ................................................... 12

2.6.1. Oxidation of Thiols ........................................... 12 2.6.2. Oxidation of Sulfides and Sulfoxides ............................ .

3. Scope and Limitations ................................................... . 3.1. Oxidation of Alkanes ............................................... . 3.2. Oxidation and Ammoxidation of Alkylaromatics ....................... . 3.3. Oxidation of Aromatic Compounds ................................... . 3.4. Oxidation of Carbon-Carbon Double Bonds ........................... . 3.5. Oxidation of Alcohols .............................................. .

3.5.1. Primary Alcohols ............................................ . 3.5.2. 2-Acetylenic Alcohols ........................................ . 3.5.3. Cyciobutanols .............................................. . 3.5.4. Phenols and Phenyl Ethers .................................... .

3.6. Carbonyl Compounds .............................................. . 3.7. Nitrogen Compounds .............................................. . 3.8. Sulfur Compounds ................................................. .

3.8.1. Thiols ..................................................... . 3.8.2. Sulfides and Sulfoxides ....................................... . 3.8.3. Disulfides .................................................. .

4. Experimental Considerations and Procedures ............................... . 4.1. General Considerations ............................................. . 4.2. General Procedures and Typical Detailed Procedures ................... .

4.2.1. Epoxidation of Carbon-Carbon Double Bonds .................. . 4.2.2. Oxidation of Alcohols ........................................ . 4.2.3. Intramolecular Oxidative Coupling of Phenols ................... . 4.2.4. Oxidation of Nitrogen Compounds ............................. . 4.2.5. Oxidation of Sulfur Compounds ............................... .

4.2.5a. Synthesis of p-Hydroxysulfoxides ....................... . 4.2.5b. Oxidation of Sulfides ................................. .

References

ix

13 13 13 14 14 15 18 18 19 19 20 25 25 27 27 28 29 29 29 29 29 30 31 31 32 32 32 33

x CONn:NTS

CHAPTER 2. OXIDATION BY OXOCHROMIUM(VI) COMPOUNDS

Fillmore Freeman

I. Introduction ........................................................... . 2. Mechanisms ........................................................... .

2.1. Carbon-Hydrogen Bonds .......................................... . 2.1.1. Alkanes and CycJoalkanes .................................. . 2.1.2. Allylic Oxidations ......................................... . 2.1.3. Benzylic Oxidations ........................................ .

2.2. Carbon-Carbon Double Bonds ..................................... . 2.3. Hydroxy Compounds .............................................. .

2.3.1. Alcohols ................................................. . 2.3.2. Diols .................................................... .

2.4. Ethers 2.5. Carbonyl Compounds ............................................. .

2.5.1. Aldehydes ....................... " ...................... . 2.5.2. Ketones ................................................. .

2.6. Carboxylic Acids .................................................. . 2.7. Nitrogen Compounds ............................................. . 2.8. Sulfur Compounds ................................................ . 2.9. Organic Halides .................................................. .

3. Scope and Limitations ................................................... . 3.1. Oxidation of Alkanes and CycJoalkanes .............................. . 3.2. Oxidation of Allylic Carbon-Hydrogen Bonds ........................ . 3.3. Oxidation of Carbon-Hydrogen Bonds Adjacent to Triple Bonds ........ . 3.4. Oxidation of Alkylbenzenes ........................................ . 3.5. Oxidation of Hydrindacenes. Indans. Tetralins. and Acenaphthenes ...... . 3.6. Oxidation of Aromatic Rings ....................................... . 3.7. Oxidation of Unsaturated Systems ................................... .

3.7.1. Nonfunctionalized Alkenes and Polyenes ...................... . 3.7.2. Functionalized Alkenes ..................................... . 3.7.3. Alkynes ................................................. .

3.8. Oxidation of Hydroxy Compounds .................................. . 3.8.1. Alcohols ................................................. . 3.8.2. Carbohydrates ............................................ . 3.8.3. Phenols ................................................. .

3.9. Oxidation of Ethers ............................................... . 3.10. Oxidation of Silyl Ethers ........................................... . 3.11. Oxidation of Carbonyl Compounds .................................. .

3.11.1. Aldehydes ............................................... . 3.11.2. Ketones ................................................. .

3.12. Oxidation of Carboxylic Acids and Their Derivatives ................... . 3.12.1. Carboxylic Acids .......................................... . 3.12.2. Esters ................................................... .

3.13. Oxidation of Nitrogen Compounds .................................. . 3.13.1. Amines .................................................. . 3.13.2. Amides .................................................. . 3.13.3. Oximes .................................................. . 3.13.4. Imines ................................................... .

3.14. Oxidation of Sulfur Compounds .................................... . 3.15. Oxidation of Organic Halides ....................................... . 3.16. Oxidation of Organoboranes ....................................... .

4. Experimental Considerations and Procedures ............................... . 4.1. General Considerations ............................................ .

41 43 43 43 44 44 45 46 46 47 47 48 48 48 48 48 49 49 49 49 50 52 53 56 57 59 59 66 67 68 68 81 81 82 85 86 86 87 87 87 87 88 88 92 92 92 93 93 94 96 96

CoNTENTS xi

4.2. General Procedures and Typical Detailed Procedures .................. . 96 96 97 98 99

4.2.1. Carbon-Hydrogen Bonds ................................... . 4.2.2. Allylic Carbon-Hydrogen Bonds ............................. . 4.2.3. Alkylaromatics ........................................... . 4.2.4. Indans and Tetralins ....................................... . 4.2.5. Alkenes .................................................. . 4.2.6. Alcohols ................................................. . 4.2.7. Benzyl Ethers ............................................. . 4.2.8. Silyl Ethers ............................................... . 4.2.9. Trialkyloxyboroxines ...................................... . 4.2.10. Esters ..................... . ............................ . 4.2.11. Oximes .................................................. . 4.2.12. Organoboranes ........................................... .

References

CHAPTER 3. THE OXIDATION OF ORGANIC COMPOUNDS BY

AcnVE MANGANESE DIOXIDE

Alexander J. Fatiadi

100 102 106 106 106 107 107 107 108

1. Introduction ............................................................ 119 1.1. Types and Methods of Preparation of Active Manganese Dioxide ......... 120

1.1.1. Standardization of Active Manganese Dioxide .................. 121 1.1.2. Preparation of Very Active Manganese Dioxide ................. 121 1.1.3. Preparation of Active Manganese Dioxide. . . . . . . .. . . . . . .. . . . . .. 121 1.1.4. Preparation of Active ')I-Manganese Dioxide .................... 122

1.2. Effects of Solvent on Oxidation ...................................... 122 1.3. Time and Temperature Effects on Oxidation ........................... 123 1.4. Structure of Active Manganese Dioxide ............................... 123

2. Mechanism ............................................................. 124 2.1. Free-Radical Mechanism ...................................... " . . .. 124 2.2. Ionic Mechanism .................................................. 126

2.2.1. Cyclic Transition Intermediate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 126 2.2.2. Manganic Ester Intermediate................................. 126

3. Oxidation of Alcohols and Hydroxy Compounds ............................. 127 3.1. cc,p-Unsaturated Alcohols (IX,P-Ethylenic Primary and Secondary Alcohols). 127

3.1.1. Vitamin AI and Analogs..................................... 127 3.1.2. cc,P-Ethylenic. Primary and Secondary Alcohols ................. 128 3.1.3. Oxidation of cis- and trans-Unsaturated Alcohols ............... 131 3.1.4. lX,p-Unsaturated Lactones ........... " . ... . .. . . . . . . . . . . . . . . .. 134 3.1.5. Additional Pertinent Oxidations .............................. 138 3.1.6. lX,p-Unsaturated Diols and Polyols ............................ 139 3.1.7. Conjugative Activation of IX-Hydroxyl Groups in Unsaturated

Alcohols .................................................. 140 3.1.8. Oxidation of cc,p-Unsaturated Aldehydes ....................... 143

3.2. Acetylenic Alcohols ................................................ 144 3.2.1. lX,p-Unsaturated Acetylenic Alcohols .......................... 144 3.2.2. Oxidation of Alkynic Alcohols of Type R-CHOH-C::CH ...... 146 3.2.3. Oxidation of Acetylenic Alcohols in the Presence of Amines ....... 149

3.3. Terpenes ....................................................... " 149 3.3.1. The Stereospecific Corey Esterification ......................... 149 3.3.2. Selective Oxidations of Terpenes .............................. 149 3.3.3. Synthesis of Sesquicarene .................................... 152 3.3.4. Rearrangement of Terpenes .................................. 152

xii

3.4.

3.5. 3.6.

3.7. 3.8. 3.9. 3.10.

3.11.

3.12.

CONTENTS

Steroids ......................................................... . 3.4.1. Oxidation of Unsaturated Steroid Alcohols in Ring A, B, C, or D .. 3.4.2. Steroidal Alkaloids ........................................ .

3.4.2a. Oxidation of an Active Methylene Group in Solacon-gestidine .......................................... .

3.4.2b. Active Manganese Dioxide: A Reagent for a Biomimetic Cyciization ....................................... .

Alkaloids Benzylic Alcohols ................................................. . 3.6.1. Oxidation of Phthalyl Alcohols .............................. . 3.6.2. Oxidation of Benzenemethanols .............................. . 3.6.3. Favored Oxidation of Benzylic Hydroxyl Groups ............... . 3.6.4. Oxidation in the Vitamin D Series ........................... . 3.6.5. Conversion of ex-Hydroxy Acids into Keto Acids ............... . Heterocyclic Alcohols ............................................. . Saturated Aliphatic Alcohols ....................................... . Polyhydroxy Compounds .......................................... . Carbohydrates ................................................... . 3.1 0.1. Synthesis of Alditols ....................................... . 3.10.2. Application of the Corey Procedure .......................... . 3.10.3. Application of the Mannich Base ............................. . 3.10.4. Other Applications ........................................ . Phenols ......................................................... . 3.11.1. Oxidative Coupling of Phenols .............................. . 3.11.2. Oxidative Polymerization of Phenols ......................... . Benzilic Acid Type Rearrangements .................................. . 3.12.1. Oxidative Ring Contraction of Carotenoid Diosphenols ......... . 3.12.2. Oxidative Ring Contraction of Steroids ....................... .

153 153 156

156

156 157 157 159 160 161 166 166 167 169 172 172 174 174 175 175 178 178 182 186 187 188

4. Dehydrogenation and Oxidative Aromatization .............................. 189 4.1. Dehydrogenation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 189

4.1.1. Dehydrogenation at Carbon or Carbon-Hetero Atom .......... , .. 190 4.1.2. Dehydrogenation in the Diazepine Series ....................... 193

4.2. Oxidative Aromatization ............................................ 195 5. Hydrocarbons .......................................................... 198

5.1. Some Chemical Applications of Precipitated Manganese Dioxide in Acid Media (e.g., Oxidation of Conjugated CH J -, CH 2 -, and = CH - Groups) 198 5.1.1. Aromatic Systems .......................................... 198 5.1.2. Other Systems ............................................. 199

5.2. Oxidation of Conjugated CH 3 -, CH ~ -. and = C - Groups by Manganese Dioxide in Neutral Media ........................................... 200 5.2.1. Oxidation of Heteroaromatic Rings. Loss of Aromaticity ......... 202 5.2.2. Oxidation of Alkyl Ferrocenes and Bridged Ferrocenes ........... 202

6. Amines and Hydrazines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 204 6. 1. Amines .......................................................... 204

6.1.1. Primary and Secondary Amines Including Anilines .............. 205 6.1.2. Oxidative Cyciization of Ortho-Substituted Anilines . . . . . . . . . . . . .. 208 6.1.3. Dehydrogenation of Amines. Rearrangements ................... 210 6.1.4. Ring Transformation of Aryl 1,2-Diaminoimidazole ............ .. 211 6.1.5. Synthesis of ex-Diketones and Pyrazine Derivatives from ex-Ami no-

ketones ................................................... 212 6.1.6. Tertiary Amines ............................................ 212 6.1.7. Hydroxylamines and Oximes ................................. 214 6.1.8. Cyano-anils from Aminonitriles ............................... 217

6.2. Hydrazines and Their Derivatives .................................... 218

CONTENTS xiii

6.2.1. H ydrazines ................................................ 218 6.2.2. Hydrazides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 218 6.2.3. Azines. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 220 6.2.4. Hydrazones. . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 220 6.2.5. oe-Diazoketones. Useful Synthetic Intermediates ................. 223 6.2.6. Lactams by Intramolecular Ene Insertion of Acylazocarboxylates .. 224 6.2.7. Phenylhydrazones. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 224

7. Miscellaneous Oxidations ................................................. 226 7.1. Nitriles .......................................................... 226 7.2. Indoles and Carbazoles ............................................. 228 7.3. Oxidative Dimerization of Heterocyclic Compounds .................... 228 7.4. Nucleic Acid Derivatives ............................................ 229 7.5. Organic Sulfides ................................................... 229 7.6. Phosphorous Compounds ........................................... 231 7.7. Other Applications ................................................. 232 7.8. MisceUaneous Recent Results ........................................ 233

8. Experimental Procedures ................................................. 236 8.1. Preparation of 2-Formylchromone ................................... 236 8.2. Oxidation of Gibberellic Acid with MnO~ ............................. 236 8.3. Preparation of 2-Methyl-2(2' -methyl-I' -propenoxy )-propionaldehyde and

Tetramethylsuccinaldehyde from Isobutyraldehyde ...................... 236 8.4. Conversion of Geraniol into Methyl Geranate .......................... 237 8.5. Preparation of 1-( 4-Acetoxy-2.6.6-trimethyl-2-cyclohexen-l-yl) 2( E )-buten-I-

one .............................................................. 237 8.6. Manganese Dioxide Oxidation of Solacongestidine ...................... 237 8.7. Oxidation of Exo-aUylic Alcohol to the Ketone. . . . . . . . . . . . . . . . . . . . . . . .. 237 8.8. Oxidation of DL-4-Hydroxy-3-methoxymandelic Acid to Keto Acid ....... 237 8.9. Preparation of 2'. 3'-O-Isopropylidene-S'-oxo-6.S'-cyclouridine ........... 238 8.10. General Procedure for Dehydrogenation of 4.S-Dihydro-1.2-oxazoles ...... 238 8.11. Preparation of 7.7.8.8-Tetracyanoquinonedimethane. TCNQ ............. 238 8.12. Preparation of oe-Cyanoglyoxylidenedi-o-toludine ....................... 238 8.13. Oxidation of m-Nitrobenzylidene-o-phenylenediamine ................... 238 8.14. Oxidation of o-(p-Nitrobenzylideneamino)-phenol ...................... 239 8.15. Oxidation of 3-Hydroxyanthranilic Acid. . . . . . . . . . . . . . . .. . . . . . . . . . . . . .. 239 8.16. Preparation of 1,3-bis [oe-diazobenzyl] Benzene ........................ 239 8.17. Synthesis of 4-Diazo-I.2.S.6-tetramethyltricyclo-[3.1.0.02•6 ] Hexan-3-one ... 239 8.18. Specific Oxidation of myo-lnosose Phenyl hydrazone .................... 240 8.19. Dimethyl ent-3oe. 13-Dihydroxy-2-oxo-20-norgibberella-I(IO). 16-diene-7.19-

dioate ........................................................... 240 8.20. Preparation of Methyl(Z )-6-oxo-2-hepten-4-ynoate ..................... 240 8.21. Preparation of 3-(2-Deoxy-3.5-di-O-p-toluol-tJ-D-erytropentofuranosyl )-6.7-

dihydroimidazo[ 4.5-d] [1.3 ]diazepin-8( 3H )-one ........................ 240 8.22. Preparation of 6-Methoxy-4-methylbenzofuran-2-carbaldehyde ........... 240 8.23. Preparation of 8-Methoxy-3,4-dihydroisoquinoline ...................... 240 8.24. Preparation of Azobis( Benzocrown Ether) ............................. 241 References .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 241

CHAPTER 4. REACTIONS WITH MANGANESE(III) ACETATE

w. J. de Klein

I. Introduction ............................................................ 261 2. Synthesis and Properties of Manganese (1lI) Acetate .......................... 262

xiv CONnNTS

2.1. Anhydrous Manganese (III) Acetate .................................. 263 2.2. Manganese (III) Acetate Dihydrate ................................... 266

3. Oxidative Addition Reactions of Acids to Olefinic Unsaturated Systems. . . . . . . . .. 266 4. Mn(II1l Acetate-Initiated Addition of Aldehydes to Olefinic Unsaturated Systems . 270 5. Mn(III) Acetate-Initiated Addition of Ketones to Olefinic Unsaturated Systems. .. 273

5.1. Formation of Higher Saturated. Unsaturated. and Acetoxy-Ketones ....... 273 5.2. Formation of Dihydrofurans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 283 5.3. Formation of Tetralones ............................................ 285 5.4. Formation of 1.4-Diketones ......................................... 286

6. M n( III) Acetate-Acetone - Initiated Addition of Haloalkanes to Unsaturated Systems ..... ....... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 286

7. Aromatic Substitution Reactions ........................................... 287 7.1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 287 7.2. Oxidative Carboxymethylation ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 287 7.3. Oxidative Aromatic Substitution by Ketones ........................... 287 7.4. Oxidative Nitromethylation ......................................... 289

8. Direct Oxidation Reactions with Manganese (III) Acetate ..................... 290 8.1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 290 8.2. Alcohols ......................................................... 290 8.3. Amino Compounds ................................................ 291 8.4. Thio Compounds .................................................. 292 8.5. Phenols. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 292 8.6. Carboxylic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 293 8.7. Aromatic Ethers ................................................... 294 8.8. Aromatic Hydrocarbons ............................................ 296 8.9. Terpenes, Cycloaliphatic Compounds. Saturated and Unsaturated Hydro-

carbons .......................................................... 300 8.10. Carbonyl Containing Compounds .................................... 306

I 8.11. Oxidative Coupling of - C - H Active Substrates ....................... 307

I 9. Synthetic Procedures ..................................................... 307

9.1. Synthesis of Anhydrous Manganese (III) Acetate ....................... 307 9.2. Synthesis of Manganese (III) Acetate Dihydrate ........................ 308 9.3. Oxidation of IX-Methylstyrene with Manganese (III) Acetate to }'-Methyl-

")I-Phenyl Butyrolactone ............................................. 308 9.4. Oxidation of Decene-I with in Situ Prepared Manganese (III) Acetate to

}'-n-Octylbutyrolactone ............................................. 308 9.5. Oxidation of Norbornene with Manganese (III) Acetate to the

Corresponding Lactone (2-0xo-3-methylene-4. 7-methanobenzofuran) ..... 309 9.6. Synthesis of a IX-Cyano-y-Butyro Lactone Derived from an Olefin and

Cyanoacetic Acid .................................................. 309 9.7. Oxidation of I-Octene with Manganese (III) Acetate/Copper (II) Acetate to

4-Decenoic Acid ................................................... 309 9.8. Conversion of I-Octene with Manganese (III) Acetate to Decanoic Acid ... 310 9.9. Oxidative Addition of an Aldehyde to an Olefin with Mn(III) Acetate in the

Presence of Cui II) Salts. General Procedure for the Preparation of Unsaturated Aldehydes ............................................. 310

9.10. Addition of Cyclopentanone to Isobutylene with Mn(lII) Acetate to 2-Isobutylcyciopentanone ........................................... 310

9.11. Mn(III) Acetate-Initiated Addition of Acetone to I-Hexene. Formation of Methyl-heptylketone ............................................... 310

9.12. Oxidative Addition of Acetylacetone to !X-Methylstyrene with Mn(III) Acetate to 2,5-Dimethyl-3-acetyl-5-phenyl-dihydrofuran ................. 311

CONn:NTS xv

9.13. Addition of Cyclohexanone to Isopropenylacetate with Mn( III) Acetate to 2-Acetonyl-cyclohexanone .......................................... .

9.14. Mn(III) Acetate-Initiated Addition of Carbontetrachloride to 1-0ctene with Formation of 1,1,I-Trichloro-3-chlorononane from 1-0ctene, Carbon-tetrachloride, and Mn(OAc)3 ....................................... .

9.15. Oxidative Addition of Acetone to Benzene with Manganese (III) Acetate to Yield Methylbenzyl Ketone from Benzene, Acetone, and Mn(OAch ...... .

9.16. Oxidative Addition of Nitromethane to Benzene with Manganese (III) Acetate to Yield Phenylnitromethane ................................ .

References ............................................................ .

CHAPTER 5. OXIDATIONS BY COBALT COMPOUNDS

Fillmore Freeman

311

311

311

312 312

1. Introduction ............................................................ 315 2. Mechanisms ............................................................ 316

2.1. Carbon-Hydrogen Bonds ........................................... 316 2.1.1. Alkanes and Cycloalkanes ................................... 316 2.1.2. Benzylic Oxidations ......................................... 320 2.1.3. Tetralins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 321 2.1.4. Allylic Oxidations .......................................... 321

2.2. Arenes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 322 2.3. Carbon-Carbon Double Bonds ...................................... 322 2.4. Carbon-Carbon Triple Bonds ....................................... 324 2.5. Organic, Organomagnesium. and Organomercuric Halides ............... 327 2.6. Hydroxy Compounds .............................................. , 328

2.6.1. Alcohols. . . . . . .. . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . .. 328 2.6.2. Diols. . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 328 2.6.3. Carbohydrates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 329 2.6.4. Phenols and Hydroquinones ................................. 329

2.7. Oxiranes. . . . . .. . .. . . .. . . . . . . . . . . . . . . .. . . . . . . . . . .. . . . . . . . . . . . . . . .. 332 2.8. Carbonyl Compounds .............................................. 332

2.8.1. Aldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 332 2.8.2. Ketones and o-Quinones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 333

2.9. Carboxylic Acids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 334 2.10. Nitrogen Comounds ................................................ 334 2.11. Phosphorus Compounds ............................................ 336 2.12. Sulfur Compounds ................................................. 336

3. Scope and Limitations .................................................... 336 3.1. Oxidation of Alkanes and Cycloalkanes ............................... 336 3.2. Oxidation of Alkylbenzenes ......................................... 337 3.3. Oxidation of Tetralins .............................................. 341 3.4. Allylic Oxidations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 341 3.5. Oxidation of Arenes ................................................ 341 3.6. Oxidation of Carbon-Carbon Double Bonds ........................... 342 3.7. Oxidation of Carbon-Carbon Triple Bonds ............................ 342 3.8. Oxidation of Organic, Organomagnesium. and Organomercuric Halides ... 351 3.9. Oxidation of Hydroxy Compounds ................................... 352

3.9.1. Alcohols. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 352 3.9.2. Oxidation of Diols ......................................... 353 3.9.3. Oxidation of Phenols and Hydroquinones ..................... 353

3.10. Oxidation of Oxiranes .............................................. 355

xvi CON'reNTS

3.11. Oxidation of Carbonyl Compounds .................................. . 3.11.1. Aldehydes ............................................... . 3.11.2. Oxidation of Ketones and o-Quinones ........................ .

3.12. Oxidation of Nitrogen Compounds .................................. . 3.12.1. Amines .................................................. . 3.12.2. Amides .................................................. . 3.12.3. Hydrazones and Oximes .................................... . 3.12.4. N itrosobenzenes .......................................... . 3.12.5. Isocyanides .............................................. .

3.13. Oxidation of Sulfur Compounds .................................... . 4. Experimental Considerations and Procedures ............................... .

4.1. General Considerations ............................................ . 4.2. General Procedures and Typical Detailed Procedures .................. .

4.2.1. Alkylbenzenes ............................................ . 4.2.2. Allylic Oxidation .......................................... . 4.2.3. Alkenes .................................................. . 4.2.4. Alkynes " ............................................... . 4.2.5. Organic Halides ........................................... . 4.2.6. Phenols and Hydroquinones ................................ .

References

CHAPTER 6. OXIDATION OF ORGANIC COMPOUNDS WITH

NICKEL PEROXIDE

M. V. George

t. Introduction ........................................................... . 2. Mechanism of Oxidation ................................................. . 3. Scope and Limitations ................................................... .

3. t. Alcohols ........................................................ . 3. I. t. Oxidation in Aqueous Alkaline Medium ...................... . 3.1.2. Oxidation in Organic Solvents ............................... .

3.2. Phenols ......................................................... . 3.3. Hydroxy Compounds Containing Other Functionalities ................ . 3.4. Carbonyl Compounds ............................................. . 3.5. Amines ......................................................... .

3.5.1. Primary Amines ........................................... . 3.5.2. Secondary Amines ......................................... .

3.6. Hydrazines ...................................................... . 3.7. Hydroxylamines .................................................. . 3.8. Hydrazones. Phenylhydrazones. Benzoylhydrazones. and Oximes ........ . 3.9. Schiff Bases ...................................................... . 3.10. Compounds Containing Activated C - H Bonds ....................... . 3.11. Sulfur Compounds ................................................ . 3.12. Miscellaneous Reactions ........................................... .

3.12.1. Dehydrogenation and Other Reactions of Heterocycles .......... . 3.12.2. Telomerization and Polymerization Reactions ................. .

4. Experimental Considerations ............................................. . 4.1. Nickel Peroxide .................................................. . 4.2. Reaction Conditions ............................................... . 4.3. Workup Procedures ............................................... . 4.4. Model Experimental Procedures .................................... .

4.4.1. Preparation of Nickel Peroxide .............................. .

355 355 355 355 355 356 357 357 358 358 360 360 360 360 360 361 361 363 364 364

373 374 377 377 378 379 383 383 384 385 385 390 392 392 394 399 407 407 408 408 410 414 414 414 415 415 415

CONTENTS

4.4.2. 4.4.3. 4.4.4. 4.4.5. 4.4.6. 4.4.7. 4.4.8. 4.4.9. 4.4.10. 4.4.11. 4.4.12. 4.4.13. 4.4.14. 4.4.15. 4.4.16. 4.4.17. 4.4.18.

xvii

Determination of Available Oxygen in Nickel Peroxide ........... 415 Reactivation of Nickel Peroxide .............................. 416 Oxidation of Benzyl Alcohol in Aqueous Alkaline Medium ....... 416 Oxidation of Benzyl Alcohol in Benzene ....................... 416 General Procedure for Oxidation of Phenols. . . . . . . . . . . . . . . . . . .. 416 Oxidation of Benzoin ....................................... 416 Oxidation of Vitamin AI ..................................... 416 General Procedure for the Ammoxidation of Aldehydes .......... 416 Oxidation of 4-Hydroxy-3-phenyltriphenylmethane .............. 417 Oxidation of Cyclohexanone ................................. 417 Oxidation of o-Phenylenediamine ............................. 417 Oxidation of Benzophenone Hydrazone ........................ 417 Oxidation of Benzil Bisphenylhydrazone ....................... 417 Oxidation of o-(p-Nitrobenzylidineamino)phenol ................ 418 Oxidation of Chloroform .................................... 418 Oxidation of Methyl 2-n-Propyloxazoline-4-carboxylate .......... 418 Oxidation of Phthalic Acid Hydrazide in the Presence of 1.3-Cyclo-octadiene ................................................. 418

References ............................................................. 418

CHAPTER 7. OXIDATIONS OF ORGANIC COMPOUNDS CATALYZED BY COPPER- AND

COBALT-AMINE COMPLEXES

C. R. H. I. de Jonge

I. Introduction ............................................................ 423 2. Mechanism ............................................................. 424 3. Scope and Limitations .................................................... 426

3.1. Copper-Amine Catalyzed Oxidations .................................. 426 3.1.1. Acetylenes .................................................. 426 3.1.2. Phenols .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 427 3.1.3. Activated Methine Compounds ................................. 428 3.1.4. Miscellaneous ............................................... 428

3.2. Cobalt-Amine Catalyzed Oxidations .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 429 3.2.1. Phenols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 430 3.2.2. Oxidative Cleavage Reactions .................................. 430

4. Experimental Considerations and Procedures ................................ 430 4.1. Copper-Amine Catalysts ............................................. 430

4.1.1. Copper-TMEDA Catalyst ..................................... 430 4.2. Cobalt-Amine Catalysts ............................................. 431 4.3. Copper-Amine Catalyzed Oxidations of Organic Substrates ............... 431

4.3.1. Ethynyl Compounds: Symmetrical Oxidative Coupling (Glaser Con-ditions) ..................................................... 431

4.3.2. Ethynyl Compounds: Unsymmetrical Oxidative Coupling (Hay Con-ditions) ..................................................... 432

4.3.3. Phenols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 433 4.3.4. Activated Methine Compounds ................................. 434 4.3.5. Miscellaneous ............................................... 435

4.4. Oxidative Cleavage. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 436 4.5. Cobalt-Amine Catalyzed Oxidations of Organic Substrates ............... 436

4.5.1. Phenols: Oxygenation ......................................... 436 4.6. Oxidative Cleavage ................................................. , 437

xviii CONTENTS

5. Tabular Survey of Oxidations of Organic Compounds Catalyzed by Copper- and Cobalt-Amine Complexes ................................................. 439 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 442

CHAPTER 8. RUTHENIUM TETROXIDE OXIDATIONS

John L. Courtney

I. Introduction ............................................................ 445 2. The Mechanism of Ruthenium Tetroxide Oxidations .......................... 446

2.1. Ionic Reactions .................................................... 446 2.1.1. Oxidation of Alcohols ........................................ 446 2.1.2. Oxidation of Ethers .......................................... 446 2.1.3. Oxidation of N6.~-Dialkyl Adenosines ......................... 447 2.1.4. Oxidation of Naphthalenes .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 447

2.2. Reactions Involving Free Radicals .................................... 448 2.2.1. Oxidation of Chlorophenols and Arylfurans ..................... 448 2.2.2. Oxidation of Alkenes ........................ . . . . . . . . . . . . . . . .. 449 2.2.3. Oxidation of Cyc10alkanes ................................... .

3. Scope and Limitations ................................................... . 3.1. Oxidation of Alcohols ............................................. . 3.2. Oxidation of Aldehydes ............................................ . 3.3. Oxidation of Ethers ............................................... . 3.4. Oxidation of Amines, Amides, and Nitrogen Heterocyclic Compounds .... . 3.5. Oxidation of Organic Sulfides ....................................... . 3.6. Oxygen Insertion Reactions of Ruthenium Tetroxide ................... . 3. 7. Oxidation of Carbon-Carbon Double Bonds .......................... . 3.8. Oxidation of Alkynes .............................................. . 3.9. Oxidation of Aromatic Systems ..................................... . 3.10. Oxidation of Cyc10alkanes ......................................... .

4. Experimental Considerations and Procedures ............................... . 4.1. Preparation of Ruthenium Tetroxide ................................. . 4.2. General Methods of Oxidation with Ruthenium Tetroxide .............. . References

CHAPTER 9. OXIDATIONS USING PALLADIUM COMPOUNDS

Suzanne F. Davison and Peter M. Maitlis

449 450 450 452 452 453 457 457 458 460 461 463 463 464 464 466

I. Introduction ............................................................ 469 2. Oxidation of Olefins .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 471

2. I. Oxidation of Ethylene in Water ....................................... 471 2.2. Oxidation of Ethylene in Acetic Acid ................................. .. 473 2.3. Oxidation of Ethylene in Alcohols ..................................... 474 2.4. Oxidation of Higher Olefins in Water .................................. 475 2.5. Oxidation of Higher Olefins in Acetic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 477 2.6. Oxidation of Higher Olefins in Alcohols ................................ 477

3. Vinylic Substitution Reactions ............................................. 480 3.1. Olefin Arylation .................................................... 480

3.1.1. Mechanisms ................................................. 481 3.2. The Heck Reaction .................................................. 482

CONnNTS xix

4. Aromatic Substitution Reactions ........................................... 488 4.1. Arene Coupling and Related Reactions ................................. 488 4.2. Aromatic Acetoxylation Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 491 4.3. Mechanisms ....................................................... 492

5. Oxidative Carbonylations ................................................. 493 5.1. Oxidative Carbonylation of Olefins .................................... 493

5.1.1. Mechanisms ................................................. 495 5.2. Oxidative Carbonylation of Aromatics ................................. 496

6. Some Reactions of Alcohols ............................................... 496 6.1. Oxidation ......................................................... 496 6.2. Oxidative Carbonylation ............................................. 497

7. Examples .............................................................. 498 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 500

CHAPTER 10. SILVER CARBONATE ON CELITE OXIDATIONS

Marcel Felizon, Michel Golfier. Philippe Mourgues. and Jean-Mc.rie Louis

1. Introduction ............................................................ 503 2. Mechanism ............................................................. 505 3. Scope and Limitations .................................................... 507

3.1. Protecting Groups ................................................. 507 3.2. Oxidation of Monoalcohols ......................................... 507 3.3. Lactones from Diols ................................................ 509 3.4. Lactones from Lactols .............................................. 519 3.5. Hydroxy Ketones from Diols. Cleavages of iX-Diols . . . . . .. .. . . . . . . . . . . . .. 519 3.6. Steroids. Di- and Triterpenes ........................................ 519 3.7. Carbohydrates. . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . .. 542

3.7.1. Regioselectivity ............................................. 542 3.7.2. Degradation .... . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . .. .. 542

3.8. Oxidation of Phenols ............................................... 543 3.8.1. Formation of Quinones. .. . . .. .. . . .. .. . . . . . . .. .. .. .. . . . . .. . . .. 543 3.8.2. Oxidative Coupling of Phenols ................................ 545

3.9. Aliphatic Amines .................................................. 549 3.10. Aromatic Amines .................................................. 550 3.11. Hydrazine Derivatives .............................................. 552 3.12. Hydroxylamines ................................................... 552 3.13. Oximes ..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 552 3.14. Fragmentation Reactions ........................................... 555 3.15. Rearrangements: Halohydrins ....................................... 555 3.16. Miscellaneous Reactions ............................................ 555

4. Experimental Procedures ................................................. 560 4.1. Silver Carbonate on Celite Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 560 4.2. Recovery of Silver Nitrate ........................................... 560 4.3. Oxidation of 2-(3-Cyc1ohexenyl)-l-Propanol ........................... 561 4.4. Oxidation of 4-Hydroxydendrolasin to (E)-9-(Furan-3'-yl)-2.6-Dimethynona-

2.6-dien-4-one ..................................................... 561 4.5. Oxidation of 3-Methylpentane-l.3.5-triol to Mevalonolactone ............ 561 4.6. Oxidation of 2.6-Dimethylphenol to 3.3'.5.5'-Tetramethyldiphenoquinone .. 562 4.7. Oxidation of Benzaldehyde Oxime to 3.5-Diphenyl-I,2.4-0xadiazole ...... 562 References .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 562

xx CONTENTS

CHAPTER 11. CERIUM(IV) OXIDATION OF ORGANIC COMPOUNDS

Tse-Lok Ho

I. Introduction 569 2. Mechanism ............................................................. 570

2.1. General Considerations .............................................. 570 2.2. C-H Bond Fission Reactions ......................................... 571 2.3. C-C Bond Cleavage Reactions ........................................ 571 2.4. 1.5-Hydrogen Transfer. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 574 2.5. Oxidation of Aromatic Compounds ..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 574 2.6. Additive Oxidation .................................................. 575 2.7. Miscellaneous ...................................................... 576

3. Scope and Limitations .................................................... 576 3.1. General Aspects .................................................... 576 3.2. Alcohols .......................................................... 577 3.3. Carbonyl Compounds and Derivatives ................................. 580

3.3.1. Aldehydes .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 580 3.3.2. Cyclic Ketones ............................................... 581 3.3.3. fJ-Keto Esters and Stabilized Anions. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 581 3.3.4. Oximes and Semicarbazones ................................... 582 3.3.5. Nitronates .................................................. 582 3.3.6. Carboxylic Acids and Derivatives ............................... 582

3.4. Amines ........................................................... 583 3.5. Organosulfur Compounds ............................................ 586 3.6. Aromatic Compounds ............................................... 588

3.6.1. Quinones from Phenol Derivatives and Polycyclic Arenes ... . . . . . . .. 588 3.6.2. Miscellaneous ............................................... 591

3.7. Organometallics .................................................... 594 3.8. Miscellaneous Topics ................................................ 599 Note Added in Proof ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 600

4. Experimental Conditions and Procedures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 601 5. Tabular Survey of Oxidation Reactions ..................................... 602

References ..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 627

CHAPTER 12. OXIDATIONS OF ORGANIC COMPOUNDS WITH OSMIUM TETROXIDE

Hari Shankar Singh

I. Introduction ............................................................ 633 1.1. Chemical Nature of Osmium Tetroxide ................................ 633

2. General Mechanism of Osmium Tetroxide Oxidation Reactions ................ 634 3. Scope and Limitations .................................................... 637

3.1. Oxidation of Alkenes and Related Compounds ......................... 637 3.1.1. Noncatalytic cis-Hydroxylation of Alkenes ...................... 637 3.1.2. Catalytic cis-Hydroxylation of Alkenes .......................... 639

3.1.2a. With Hydrogen Peroxide .............................. 639 3.1.2b. With Metal Chlorates ................................. 640 3.1.2c With terr-Butyl Hydroperoxide ......................... 640 3.1.2d. With N-Methylmorpholine N-Oxide .................... 641 3.1.2e. With Sodium Periodate ............................... 641 3.1.2f. With Oxygen ........................................ 642 3.1.2g. With Sodium Hypochlorite ............................ 642

3.1.3. Oxidation of Alkenes and Related Compounds by Alkylimido­osmium Compounds " . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 642

CONn:NTS xxi

3.1.4. Oxidation of Alkenes by Chloramine-T (Osmium Catalyzed) ...... 644 3.1.5. Oxidation of Alkenes by N-chloro-N-argentocarbamates (Osmium

Catalyzed) ................................................. 644 3.2. Oxidation of Alkynes (Acetylenes) .................................... 645 3.3. Oxidation of Dienes ................................................ 645 3.4. Oxidation of Quinones ............................................. 646 3.5. Oxidation of Steroids ............................................... 646 3.6. Oxidation of Pyrans ................................................ 647 3.7. Oxidation of Alcohols and Related Compounds ........................ 647 3.8. Oxidation of Diols and Related Compounds ........................... 649 3.9. Oxidation of Aldehydes and Ketones ................................. 649 3.10. Oxidation of Hydroxy Acids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 651

3.10.1. Oxidation of Glycolic and Lactic Acids ........................ 651 3.10.2. Oxidation of Malic and Mandelic Acids ........................ 652 3.10.3. Oxidation of Tartaric Acid ................................... 652

3.11. Oxidation of Dicarboxylic Acids ..................................... 653 3.11.1. Maleic and Fumaric Acid .................................... 653 3.11.2. Oxidation of Malonic Acid ................................... 653

3.12. Osmium Tetroxide in the Biochemistry Field ........................... 654 4. Experimental Considerations and Procedures ................................ 658

4.1. Osmium Tetroxide in Alkaline Medium ............................... 658 4.2. Oxidation of Alkenes by Criegee's Method ............................. 659

4.2.1. In the Absence of Bases. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 659 4.2.2. In the Presence of Bases ...................................... 659

4.3. General Procedure for the Cleavage of Osmate-Esters ................... 659 4.4. Os04-Catalyzed cis-Hydroxylation of Alkenes . . . . . . . . .. . . .. . . . . . . . . . . .. 659

4.4.1. Oxidation ofCyc1ohexene with Os04/H202 ..................... 659 4.4.2. Oxidation with OsOJMetal Chlorates .......................... 670

4.4.2a. Oxidation of Crotonic Acid to Dihydroxybutyric Acid by Osmic Acid/Barium Chlorate .......................... 670

4.4.2b. Oxidation of Crotonic Acid with OsOJPotassium Chlorate 670 4.4.2c. Oxidation of Crotonic Acid with Osmic Acid/Silver Chlorate 671 4.4.2d. Oxidation by Gradual Addition of Silver Chlorate ........ 671

4.4.3. Oxidation of Octene to Threo-4.5-dihydroxy Octane with OsOJTert-Butyl Hydroperoxide .................. . . . . . . . . . . .. 676

4.4.4. Oxidation of Cyc10hexene to cis-cyc1ohexane- I.2-diol with Os04/N-Methyl Morpholine N-Oxide .......................... 676

4.4.5. Oxidation of Cyc10hexene to Adipaldehyde with Os04/Sodium Periodate .................................................. 677

4.5. Oxidation of Alkenes by Imido Reagent ............................... 681 4.5.1. Preparation of Tert-Butyllmido/Osmium Reagent. . . . . . .. . . . . . . .. 681 4.5.2. Oxyamination of Olefins-,-General Procedure ................... 681

4.5.2a. Bi-sulfite Method .................................... 681 4.5.2b. Lithium Aluminum Hydride Method .................... 681

4.6. Oxidation of Alkenes by OsOJChloramine-T .......................... 681 4.6.1. Phase Transfer Method ....................................... 681 4.6.2. Tert-Butyl Alcohol Method ................................... 682

4.7. Oxidation of Alkenes by Os04/N-chloro-N-argento Carbamates .......... 683 4.8. Oxidation Alkynes ................................................. 685

4.8.1. Preparation of Osmium Tetroxide-Amine Adducts ............... 685 4.8.la. Osmium(Vl) Esters from Alkynes ....................... 685 4.8.1b. Hydrolysis of the Complex OS204(04C,4HIO)(NCsHs)4 to

Benzil .............................................. 685 4.8.2. Catalytic Oxidation of Diphenylacetylene ....................... 685

xxii CON1CNTS

4.9. Oxidation of Dienes ................................................ 685 4.9. I. Preparation of OsO 4/Pyridine Complexes OS2 0 4( 0 4 R) L4 ........ 686

4.10. Oxidation of Quinones ............................................. 686 4.11. Oxidation of Steroids ............................................... 686 4.12. Oxidation of Pyrane .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 686 4.13. Synthesis of a (J-Keto Aldehyde from a /J.y-Unsaturated Ketone. . . . . . . . . .. 687 4.14. Synthesis of Methyl-7-(2-hydroxy-5-oxo-l-pyroridinyl) Heptonoate ....... 687 4.15. Synthesis of (1 'Rs, 2'Rs )-8-oxo-3 endo-(1', 2' -dihydroxyheptyl )tricyclo-

4.3.0.0 nonane ................ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 687 4.16. Synthesis of "K-Region" Diepoxide ................................... 688 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 688

CHAPTER 13. THALLlUM(III) SALTS AS OXIDANTS IN ORGANIC SYNTHESIS

Alexander McKillop and Edward C. Taylor

I. Introduction ............................................................ 695 2. Scope and Limitations .................................................... 696

2.1. One-Electron Transfer Reactions ...................................... 696 2.1.1. Dehydrodimerization of Aromatic Compounds. . . . . . . . . . . . . . . . . . .. 697 2.1.2. Intramolecular Cyclizations .................................... 698 2.1.3. Oxidation of Porphyrins ....................................... 707

2.2. Two-Electron Transfer Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 709 2.2.1. Oxythallation Reactions. General Features ....................... 709 2.2.2. Oxythallation of Double and Triple Bonds ....................... 710 2.2.3. Oxidation of Nitrogen Compounds ................ . . . . . . . . . . . . .. 720 2.2.4. Oxidation of Organosulfur Compounds .......................... 722

2.3. Reactions of Uncertain Mechanisms. Oxidation of Phenols and Derivatives .. 724 3. Experimental Considerations and Procedures ................................ 729

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 736

CHAPTER 14. OXIDATIONS WITH LEAD TETRAACETATE

Mihailo Lj. Mihailovii:, livorad Cekovii:. and Ljubinka Lorenc

I. Introduction ........................................................... 741 2. Hydrocarbons ......................................................... 742

2.1. Saturated Hydrocarbons ............................................ 742 2.1.1. Mechanism ..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 742 2.1.2. Scope and Limitations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 742

2.2. Unsaturated Hydrocarbons. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 743 2.2.1. Mechanism ................................................. 744 2.2.2. Scope and Limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 744

2.2.2a. Acyclic Oletins ....................................... 744 2.2.2b. Cyclic Oletins ...................... . . . . . . . . . . . . . . . . .. 747 2.2.2c. Polycyclic Oletins and Terpenes ........................ 748 2.2.2d. Dienes and Polyenes .................................. 750 2.2.2e. Allenes and Acetylenes ................................ 753

2.3. Aromatic Hydrocarbons ............................................ 753 2.3.1. Mechanism .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 754 2.3.2. Scope and Limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 754

2.3.2a. Aromatic Rings ...................................... 754 2.3.2b. Benzylic Groups ..................................... 755

CON11ONTS xxiii

2.4. Vinyl Ethers and Enamines .......................................... 756 3. Monohydroxylic Alcohols ................................................ 758

3.t. Intramolecular Cyclization to Cyclic Ethers ............................ 759 3.1.1. Saturated Alcohols. . . . . . . . . .. . . . . . . . . . . . . . . . .. . .. . . . . . . . . . . .. 759

3.1.1a. Mechanism ......................................... 760 11.1 b. Scope and Limitations ................................ 765

3.1.2. Unsaturated Alcohols ........................................ 771 3.1.2a. Mechanism ......................................... 771 3.1.2b. Scope and Limitations ................................ 771

3.2. p-Fragmentation .................................................. 772 3.2.1. Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 772 3.2.2. Scope and Limitations .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 772

3.3. Oxidation to Carbonyl Compounds .................................. 775 3.11. Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 775 3.3.2. Scope and Limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 775

4. 1.2-Diots and Potyols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 776 4.1. Mechanism ....................................................... 777 4.2. Scope and Limitations .............................................. 777

5. Phenols ............................................................... 781 5.1. Mechanism ....................................................... 781 5.2. Scope and Limitations .............................................. 782

6. Carbonyl Compounds ................................................... 783 6.1. Mechanism ....................................................... 784 6.2. Scope and Limitations .............................................. 785

7. Carboxylic Acids ....................................................... 787 7.1. Mechanism ....................................................... 787 7.2. Scope and Limitations .............................................. 788

8. Nitrogen-Containing Compounds ......................................... 795 8.1. Amines .......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 795 8.2. Amides ..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 797 8.3. Hydrazines ....................................................... 797 8.4. Oximes .......................................................... 798 8.5. Hydrazones .. . . . . ... .. . . . . . . .. . . . . . . . . . . . . . . .. . . . . . . .. . . . . . . .. . .. 799

9. Experimental Considerations and Procedures ............................... 801 9.1. Hydrocarbons .................................................... 801 9.2. Monohydroxylic Alcohols ........................................... 802 9.3. 1.2-Diols and Polyols ............................................... 804 9.4. Phenols .......................................................... 804 9.5. Carbonyl Compounds .............................................. 805 9.6. Carboxylic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 805 9.7. Nitrogen-Containing Compounds .................................... 805

10. Addendum ............................................................. 806 tOJ. Hydroperoxides .................................................. 806 to.2. Olefinic Dicarboxylic Acids ......................................... 806 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 807

CHAPTER 15. BISMUTH-SALT OXIDATIONS

Jonathan Peter Kitchin

I. Introduction ............................................................ 8 I 7 2. Sodium Bismuthate Oxidations ............................................ 818

2.1. Mechanism and Scope. . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . .. 818

xxiv CONnNTS

2.2. Experimental Considerations and Procedures ........................... 819 2.2.1. Availability of the Reagent ..................................... 819 2.2.2. I.2-Diol and Related Oxidations ................................ 819 2.2.3. Oxidation of Phenols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 820 2.2.4. Oxidation of Olefins .......................................... 824

3. Bismuth Trioxide Oxidations .............................................. 824 3.1. Mechanism and Scope ............................................... 824 3.2. Experimental Considerations and Procedures ........................... 825

4. Organobismuth Reagents ................................................. 825 4.1. Mechanism and Scope ............................................... 825 4.2. Experimental Considerations and Procedures ........................... 828

4.2.1. Preparation of the Reagents .................................... 828 4.2.2. Oxidation with Organobismuth Reagents ........................ 829

5. The Toxicity of Bismuth .................................................. 836 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 836

CHAPTER 16. OXIDATIONS WITH METAL COMPOUNDS AND PEROXIDES

Yoshiro Ogata and Yasuhiko Sawaki

I. Introduction ............................................................ 839 2. Mechanism ............................................................. 840

2.1. Radical Mechanism via Redox Reactions (Category a) ................... 840 2.1.1. H Abstraction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 841 2.1.2. Aromatic and Other Substitution Reactions ...................... 842 2.1.3. Addition to Double and Triple Bonds ........................... 844

2.2. Ionic Mechanism via Formation of Metallic Peroxide or Metal-Peroxide Complexes (Category b) ............................................. 844 2.2.1. Epoxidations ................................................ 844 2.2.2. Oxygenation of Sulfides and Sulfoxides .......................... 845 2.2.3. Oxygenation of Amines ........................................ 846 2.2.4. Formation of Glycols ......................................... 847

2.3. Ionic Mechanism via Lewis Acid Activation ............................. 847 3. Scope and Limitations .................................................... 848

3.1. General Considerations .............................................. 848 3.2. Oxidation of Alcohols ............................................... 848

3.2.1. Alcohols .................................................... 848 3.2.2. Cleavage of Glycols and Related Compounds ..................... 849

3.3. Oxidation of Carbonyl Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 849 3.3.1. Aldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 849 3.3.2. Ketones ..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 849

3.4. Oxidation of Double Bonds .......................................... 850 3.4.1. Epoxidation of Olefins ........................................ 850 3.4.2. Regio- and Stereoselective Epoxidations . . . . . . . .. ................ 851 3.4.3. Dihydroxylation of Olefins ..................................... 852 3.4.4. Oxidative Cleavage ........................................... 853 3.4.5. Ketones from Terminal Olefins ................................. 853 3.4.6. Oxidation of C = N Bonds ..................................... 854

3.5. Oxidation of C-H Bonds ................................... . . . . . . . . .. 854 3.5.1. Direct Hydroxylation of Aliphatic C-H Bonds .................... 854 3.5.2. Oxidation of Ethers ........................................... 855 3.5.3. Oxidation of Benzylic C-H Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 855 3.5.4. Direct Hydroxylation of Aromatic Rings ......................... 855

CONTENTS

3.5.5. Acyloxylation of Allylic C-H Bonds ............................ . 3.5.6. Acyloxylation of Other Activated Aliphatic C-H Bonds ........... . 3.5.7. Acyloxylation of Aromatic Rings ............................... .

3.6. Oxidation of Nitrogen Compounds ................................... . 3.7. Oxidation of Sulfur Compounds ..................................... . 3.8. Miscellaneous Types of Oxidation .................................... .

3.8.1. Functionalization via Ligand Transfer .......................... . 3.8.2. Alkylation and Acylation of Heteroaromatic Bases ................ . 3.8.3. Dimerization ............................................... . 3.8.4. Dehydrogenation ........................................... . 3.8.5. Decarboxylation ............................................ .

4. Experimental Considerations and Procedures ............................... . 4.1. General Comments ................................................. . 4.2. A vailability and Handling of Peroxides ................................ . 4.3. General Procedures ................................................ .

4.3.1. General Precautions ......................................... . 4.3.2. Catalysts and Solvents ....................................... . 4.3.3. Work-up Procedures ......................................... . 4.3.4. Analysis of Peroxides ......................................... .

4.4. Typical Procedures ................................................. . References ............................................................ .

xxv

855 857 857 858 859 859 859 860 860 861 861 861 861 862 863 863 863 863 864 864 870

ApPENDIX ............................ . . . . . . . . . . . . . . . . • . . . . . . . . . . . . . . . . . • .. 877

INDEX 883

ORGANIC SYNTHESES BY OXIDATION WITH METAL COMPOUNDS