Organic Syntheses by Oxidation with Metal Compounds

ISBN-13: 9781461292487 / Angielski / Miękka / 2011 / 908 str.

W. J. Mijs; C. R. H. I. De Jonge

Opis

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-contain- ing 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.

Spis treści

1. Oxidation by Vanadium Compounds.- 1. Introduction.- 2. Mechanisms.- 2.1 Alkanes, Alkylaromatics, and Aromatic Compounds.- 2.2 Carbon-Carbon Double Bonds: Synthesis of Epoxides and Glycols.- 2.3 Hydroxy Compounds.- 2.3.1 Alcohols.- 2.3.2 Phenols and Hydroquinones.- 2.4 Carbonyl Compounds: Ketones and Quinones.- 2.5 Nitrogen Compounds.- 2.6 Sulfur Compounds.- 2.6.1 Oxidation of Thiols.- 2.6.2 Oxidation of Sulfides and Sulfoxides.- 3.Scope and Limitations.- 3.1 Oxidation of Alkanes.- 3.2 Oxidation and Ammoxidation of Aikylaromatics.- 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 x-Acetylenic Alcohols.- 3.5.3 Cyclobutanols.- 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 ?-Hydroxysulfoxides.- 4.2.5b. Oxidation of Sulfides.- References.- 2. Oxidation by Oxochromium(VI) Compounds.- 1. Introduction.- 2. Mechanisms.- 2.1.Carbon-Hydrogen Bonds.- 2.1.1 Alkanes and Cycloalkanes.- 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 Cycloalkanes.- 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.- 4.2. General Procedures and Typical Detailed Procedures.- 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.- 3. The Oxidation of Organic Compounds by Active Manganese Dioxide.- 1.Introduction.- 1.1.Types and Methods of Preparation of Active Manganese Dioxide.- 1.1.1 Standardization of Active Manganese Dioxide.- 1.1.2 Preparation of Very Active Manganese Dioxide.- 1.1.3 Preparation of Active Manganese Dioxide.- 1.1.4 Preparation of Active y-Manganese Dioxide.- 1.2 Effects of Solvent on Oxidation.- 1.3 Time and Temperature Effects on Oxidation.- 1.4 Structure of Active Manganese Dioxide.- 2.Mechanism.- 2.1 Free-Radical Mechanism.- 2.2 Ionic Mechanism.- 2.2.1 Cyclic Transition Intermediate.- 2.2.2 Manganic Ester Intermediate.- 3.Oxidation of Alcohols and Hydroxy Compounds.- 3.1.?,?-Unsaturated Alcohols (?,?-Ethylenic Primary and Secondary Alcohols).- 3.1.1 Vitamin A, and Analogs.- 3.1.2 ?,? -Ethylenic, Primary and Secondary Alcohols.- 3.1.3 Oxidation of cis- and fra/w-Unsaturated Alcohols.- 3.1.4 ?,?-Unsaturated Lactones.- 3.1.5 Additional Pertinent Oxidations.- 3.1.6 ?,? -Unsaturated Diols and Polyols.- 3.1.7 Conjugative Activation of ?-Hydroxyl Groups in Unsaturated Alcohols.- 3.1.8 Oxidation of ?,?-Unsaturated Aldehydes.- 3.2.Acetylenic Alcohols.- 3.2.1 ?,?-Unsaturated Acetylenic Alcohols.- 3.2.2 Oxidation of Alkynic Alcohols of Type R - CHOH - C = CH.- 3.2.3 Oxidation of Acetylenic Alcohols in the Presence of Amines.- 3.3.Terpenes.- 3.3.1 The Stereospecific Corey Esterification.- 3.3.2 Selective Oxidations of Terpenes.- 3.3.3 Synthesis of Sesquicarene.- 3.3.4 Rearrangement of Terpenes.- 3.4.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 Cyclization.- 3.5 Alkaloids.- 3.6 Benzyiic Alcohols.- 3.6.1 Oxidation of Phthalyl Alcohols.- 3.6.2 Oxidation of Benzenemethanols.- 3.6.3 Favored Oxidation of Benzyiic Hydroxyl Groups.- 3.6.4 Oxidation in the Vitamin D Series.- 3.6.5 Conversion of ?-Hydroxy Acids into Keto Acids.- 3.7 Heterocyclic Alcohols.- 3.8 Saturated Aliphatic Alcohols.- 3.9 Polyhydroxy Compounds.- 3.10 Carbohydrates.- 3.10.1 Synthesis of Alditols.- 3.10.2 Application of the Corey Procedure.- 3.10.3 Application of the Mannich Base.- 3.10.4 Other Applications.- 3.11.Phenols.- 3.11.1 Oxidative Coupling of Phenols.- 3.11.2 Oxidative Polymerization of Phenols.- 3.12.Benzilic Acid Type Rearrangements.- 3.12.1 Oxidative Ring Contraction of Carotenoid Diosphenols.- 3.12.2 Oxidative Ring Contraction of Steroids.- 4.Dehydrogenation and Oxidative Aromatization.- 4.1.Dehydrogenation.- 4.1.1 Dehydrogenation at Carbon or Carbon-Hetero Atom.- 4.1.2 Dehydrogenation in the Diazepine Series.- 4.2.Oxidative Aromatization.- 5.Hydrocarbons.- 5.1.Some Chemical Applications of Precipitated Manganese Dioxide in AcidMedia (e.g., Oxidation of Conjugated CH3-, CH2-, and =CH-Groups).- 5.1.1 Aromatic Systems.- 5.1.2 Other Systems.- 5.2.Oxidation of Conjugated CH3 —, CH: —, and =C-Groups by ManganeseDioxide in Neutral Media.- 5.2.1 Oxidation of Heteroaromatic Rings. Loss of Aromaticity.- 5.2.2 Oxidation of Alkyl Ferrocenes and Bridged Ferrocenes.- 6.Amines and Hydrazines.- 6.1.Amines.- 6.1.1 Primary and Secondary Amines Including Anilines.- 6.1.2 Oxidative Cyclization of Or/io-Substituted Anilines.- 6.1.3 Dehydrogenation of Amines. Rearrangements.- 6.1.4 Ring Transformation of Aryl 1,2-Diaminoimidazole.- 6.1.5 Synthesis of ?-Diketones and Pyrazine Derivatives from ?-Amino-ketones.- 6.1.6 Tertiary Amines.- 6.1.7 Hydroxylamines and Oximes.- 6.1.8 Cyano-anils from Aminonitriles.- 6.2.Hydrazines and Their Derivatives.- 6.2.1 Hydrazines.- 6.2.2 Hydrazides.- 6.2.3 Azines.- 6.2.4 Hydrazones.- 6.2.5 ?-Diazoketones. Useful Synthetic Intermediates.- 6.2.6 Lactams by Intramolecular Ene Insertion of Acylazocarboxylates.- 6.2.7 Phenylhydrazones.- 7.Miscellaneous Oxidations.- 7.1 Nitriles.- 7.2 Indoles and Carbazoles.- 7.3 Oxidative Dimerization of Heterocyclic Compounds.- 7.4 Nucleic Acid Derivatives.- 7.5 Organic Sulfides.- 7.6 Phosphorous Compounds.- 7.7 Other Applications.- 7.8 Miscellaneous Recent Results.- 8.Experimental Procedures.- 8.1 Preparation of 2-Formylchromone.- 8.2 Oxidation of Gibberellic Acid with MnO:.- 8.3 Preparation of 2-Methyl-2(2’-methyl-l’-propenoxy)-propionaidehyde and Tetramethylsuccinaldehyde from Isobutyraldehyde.- 8.4 Conversion of Geraniol into Methyl Geranate.- 8.5 Preparation of l-(4-Acetoxy-2,6,6-trimethyl-2-cyclohexen-l-yl) 2(E)-buten-l-one.- 8.6 Manganese Dioxide Oxidation of Solacongestidine.- 8.7 Oxidation of Exo-allylic Alcohol to the Ketone.- 8.8 Oxidation of DL-4-Hydroxy-3-methoxymandelic Acid to Keto Acid.- 8.9 Preparation of 2’3’-0-Isopropylidene-5’-oxo-6,5’-cyclouridine.- 8.10 General Procedure for Dehydrogenation of 4,5-Dihydro-l,2-oxazoles.- 8.11 Preparation of 7,7,8,8-Tetracyanoquinonedimethane, TCNQ.- 8.12 Preparation of ?-Cyanogiyoxylidenedi-o-toludine.- 8.13 Oxidation of m-Nitrobenzylidene-o-phenylenediamine.- 8.14 Oxidation of o-(?-Nitrobenzylideneamino)-phenol.- 8.15 Oxidation of 3-Hydroxyanthranilic Acid.- 8.16 Preparation of 1,3-bis [?-diazobenzyl] Benzene.- 8.17 Synthesis of 4-Diazo-l,2,5,6-tetramethyltricyclo-[3.1.0.02.6] Hexan-3-one.- 8.18 Specific Oxidation of mvo-Inosose Phenylhydrazone.- 8.19 Dimethyl ent-3?, 13-Dihydroxy-2-oxo-20-norgibberella-l(10), 16-diene-7,19-dioate.- 8.20 Preparation of Methyl(Z)-6-oxo-2-hepten-4-ynoate.- 8.21 Preparation of 3-(2-Deoxy-3,5-di-0-p-toluol-?-D-erytropentofuranosyl)-6J-dihydroimidazo[4,5-d][l,3]diazepin-8(3H)-one.- 8.22 Preparation of 6-Methoxy-4-methylbenzofuran-2-carbaldehyde.- 8.23 Preparation of 8-Methoxy-3,4-dihydroisoquinoline.- 8.24. Preparation of Azobis(Benzocrown Ether).- References.- 4. Reactions with Manganese(III) Acetate.- 1. Introduction.- 2. Synthesis and Properties of Manganese (III) Acetate.- 2.1 Anhydrous Manganese (III) Acetate.- 2.2 Manganese (III) Acetate Dihydrate.- 3. Oxidative Addition Reactions of Acids to Olefinic Unsaturated Systems.- 4. Mn(III) Acetate-Initiated Addition of Aldehydes to Olefinic Unsaturated Systems.- 5. Mn(III) Acetate-Initiated Addition of Ketones to Olefinic Unsaturated Systems.- 5.1 Formation of Higher Saturated, Unsaturated, and Acetoxy-Ketones.- 5.2 Formation of Dihydrofurans.- 5.3 Formation of Tetralones.- 5.4 Formation of 1,4-Diketones.- 6. Mn(III) Acetate-Acetone - Initiated Addition of Haloalkanes to Unsaturated Systems.- 7. Aromatic Substitution Reactions.- 7.1 Introduction.- 7.2 Oxidative Carboxymethylation.- 7.3 Oxidative Aromatic Substitution by Ketones.- 7.4 Oxidative Nitromethylation.- 8. Direct Oxidation Reactions with Manganese (III) Acetate.- 8.1 Introduction.- 8.2 Alcohols.- 8.3 Amino Compounds.- 8.4 Thio Compounds.- 8.5 Phenols.- 8.6 Carboxylic Acids.- 8.7 Aromatic Ethers.- 8.8 Aromatic Hydrocarbons.- 8.9 Terpenes, Cycloaliphatic Compounds. Saturated and Unsaturated Hydrocarbons.- 8.10 Carbonyl Containing Compounds.- 8.11. Oxidative Coupling of -C-H Active Substrates.- 9. Synthetic Procedures.- 9.1 Synthesis of Anhydrous Manganese (III) Acetate.- 9.2 Synthesis of Manganese (III) Acetate Dihydrate.- 9.3 Oxidation of a-Methylstyrene with Manganese (III) Acetate to ?-Methyl-?-Phenyl Butyrolactone.- 9.4 Oxidation of Decene-1 with in Situ Prepared Manganese (III) Acetate to ?-w-Octylbutyrolactone.- 9.5 Oxidation of Norbomene with Manganese (III) Acetate to the Corresponding Lactone (2-Oxo-3-methylene-4,7-methanobenzofuran).- 9.6 Synthesis of a ?-Cyano-?-Butyro Lactone Derived from an Olefin and Cyanoacetic Acid.- 9.7 Oxidation of 1-Octene with Manganese (III) Acetate/Copper (II) Acetate to 4-Decenoic Acid.- 9.8 Conversion of 1-Octene with Manganese (III) Acetate to Decanoic Acid.- 9.9 Oxidative Addition of an Aldehyde to an Olefin with Mn(III) Acetate in the Presence of Cu(II) Salts. General Procedure for the Preparation of Unsaturated Aldehydes.- 9.10 Addition of Cyclopentanone to Isobutylene with Mn(III) Acetate to 2-Isobutylcyclopentanone.- 9.11 Mn(III) Acetate-Initiated Addition of Acetone to 1-Hexene. Formation of Methyl-heptylketone.- 9.12 Oxidative Addition of Acetylacetone to ?-Methylstyrene with Mn(III) Acetate to 2,5-Dimethyl-3-acetyl-5-phenyl-dihydrofuran.- 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-Octene with Formation of l,l,l-Trichloro-3-chlorononane from 1-Octene, Carbontetrachloride, 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(OAc)3.- 9.16 Oxidative Addition of Nitromethane to Benzene with Manganese (III) Acetate to Yield Phenylnitromethane.- References.- 5. Oxidations by Cobalt Compounds.- 1. Introduction.- 2. Mechanisms.- 2.1. Carbon-Hydrogen Bonds.- 2.1.1 Alkanes and Cycloalkanes.- 2.1.2 Benzylic Oxidations.- 2.1.3 Tetralins.- 2.1.4 Allyiic Oxidations.- 2.2 Arenes.- 2.3 Carbon-Carbon Double Bonds.- 2.4 Carbon-Carbon Triple Bonds.- 2.5 Organic, Organomagnesium, and Organomercuric Halides.- 2.6 Hydroxy Compounds.- 2.6.1 Alcohols.- 2.6.2 Diols.- 2.6.3 Carbohydrates.- 2.6.4 Phenols and Hydroquinones.- 2.7 Oxiranes.- 2.8 Carbonyl Compounds.- 2.8.1 Aldehydes.- 2.8.2 Ketones and o-Quinones.- 2.9 Carboxylic Acids.- 2.10 Nitrogen Comounds.- 2.11 Phosphorus Compounds.- 2.12 Sulfur Compounds.- 3. Scope and Limitations.- 3.1 Oxidation of Alkanes and Cycloalkanes.- 3.2 Oxidation of Alkylbenzenes.- 3.3 Oxidation of Tetralins.- 3.4 Allyiic Oxidations.- 3.5 Oxidation of Arenes.- 3.6 Oxidation of Carbon-Carbon Double Bonds.- 3.7 Oxidation of Carbon-Carbon Triple Bonds.- 3.8 Oxidation of Organic, Organomagnesium, and Organomercuric Halides.- 3.9 Oxidation of Hydroxy Compounds.- 3.9.1 Alcohols.- 3.9.2 Oxidation of Diols.- 3.9.3 Oxidation of Phenols and Hydroquinones.- 3.10. Oxidation of Oxiranes.- 3.11. Oxidation of Carbonyl Compounds.- 3.11.1 Aldehydes.- 3.11.2 Oxidation of Ketones and oQuinones.- 3.12. Oxidation of Nitrogen Compounds.- 3.12.1 Amines.- 3.12.2 Amides.- 3.12.3 Hydrazones and Oximes.- 3.12.4 Nitrosobenzenes.- 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.- 6. Oxidation of Organic Compounds with Nickel Peroxide.- 1. Introduction.- 2. Mechanism of Oxidation.- 3. Scope and Limitations.- 3.1. Alcohols.- 3.1.1 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.- 4.4.2 Determination of Available Oxygen in Nickel Peroxide.- 4.4.3 Reactivation of Nickel Peroxide.- 4.4.4 Oxidation of Benzyl Alcohol in Aqueous Alkaline Medium.- 4.4.5 Oxidation of Benzyl Alcohol in Benzene.- 4.4.6 General Procedure for Oxidation of Phenols.- 4.4.7 Oxidation of Benzoin.- 4.4.8 Oxidation of Vitamin A.- 4.4.9 General Procedure for the Ammoxidation of Aldehydes.- 4.4.10 Oxidation of 4-Hydroxy-3-phenyltriphenylmethane.- 4.4.11 Oxidation of Cyclohexanone.- 4.4.12 Oxidation of o-Phenylenediamine.- 4.4.13 Oxidation of Benzophenone Hydrazone.- 4.4.14 Oxidation of Benzil Bisphenylhydrazone.- 4.4.15 Oxidation of o -(?-Nitrobenzyiidineamino)phenoi.- 4.4.16 Oxidation of Chloroform.- 4.4.17 Oxidation of Methyl 2-n-Propyloxazoline-4-carboxylate.- 4.4.18 Oxidation of Phthalic Acid Hydrazide in the Presence of 1,3-Cyclo-octadiene.- References.- 7. Oxidations of Organic Compounds Catalyzed by Copper- and Cobalt-Amine Complexes.- 1. Introduction.- 2. Mechanism.- 3. Scope and Limitations.- 3.1. Copper-Amine Catalyzed Oxidations.- 3.1.1 Acetylenes.- 3.1.2 Phenols.- 3.1.3 Activated Methine Compounds.- 3.1.4 Miscellaneous.- 3.2. Cobalt-Amine Catalyzed Oxidations.- 3.2.1 Phenols.- 3.2.2 Oxidative Cleavage Reactions.- 4. Experimental Considerations and Procedures.- 4.1. Copper-Amine Catalysts.- 4.1.1. Copper-TMEDA Catalyst.- 4.2 Cobalt-Amine Catalysts.- 4.3 Copper-Amine Catalyzed Oxidations of Organic Substrates.- 4.3.1 Ethynyi Compounds: Symmetrical Oxidative Coupling (Glaser Conditions).- 4.3.2 Ethynyi Compounds: Unsymmetrical Oxidative Coupling (Hay Conditions).- 4.3.3 Phenols.- 4.3.4 Activated Methine Compounds.- 4.3.5 Miscellaneous.- 4.4 Oxidative Cleavage.- 4.5 Cobalt-Amine Catalyzed Oxidations of Organic Substrates.- 4.5.1. Phenols: Oxygenation.- 4.6. Oxidative Cleavage.- 5. Tabular Survey of Oxidations of Organic Compounds Catalyzed by Copper- and Cobalt-Amine Complexes.- References.- 8. Ruthenium Tetroxide Oxidations.- 1. Introduction.- 2. The Mechanism of Ruthenium Tetroxide Oxidations.- 2.1. Ionic Reactions.- 2.1.1 Oxidation of Alcohols.- 2.1.2 Oxidation of Ethers.- 2.1.3 Oxidation of N6,N6-Dialkyl Adenosines.- 2.1.4 Oxidation of Naphthalenes.- 2.2. Reactions Involving Free Radicals.- 2.2.1 Oxidation of Chlorophenols and Arylfurans.- 2.2.2 Oxidation of Alkenes.- 2.2.3 Oxidation of Cycloalkanes.- 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 Cycloalkanes.- 4. Experimental Considerations and Procedures.- 4.1 Preparation of Ruthenium Tetroxide.- 4.2 General Methods of Oxidation with Ruthenium Tetroxide.- References.- 9. Oxidations Using Palladium Compounds.- 1. Introduction.- 2. Oxidation of Olefins.- 2.1 Oxidation of Ethylene in Water.- 2.2 Oxidation of Ethylene in Acetic Acid.- 2.3 Oxidation of Ethylene in Alcohols.- 2.4 Oxidation of Higher Olefins in Water.- 2.5 Oxidation of Higher Olefins in Acetic Acid.- 2.6 Oxidation of Higher Olefins in Alcohols.- 3. Vinylic Substitution Reactions.- 3.1. Olefin Arylation.- 3.1.1. Mechanisms.- 3.2. The Heck Reaction.- 4. Aromatic Substitution Reactions.- 4.1 Arene Coupling and Related Reactions.- 4.2 Aromatic Acetoxylation Reactions.- 4.3 Mechanisms.- 5. Oxidative Carbonylations.- 5.1. Oxidative Carbonylation of Olefins.- 5.1.1. Mechanisms.- 5.2. Oxidative Carbonylation of Aromatics.- 6. Some Reactions of Alcohols.- 6.1 Oxidation.- 6.2 Oxidative Carbonylation.- 7. Examples.- References.- 10. Silver Carbonate on Celite Oxidations.- 1. Introduction.- 2. Mechanism.- 3. Scope and Limitations.- 3.1 Protecting Groups.- 3.2 Oxidation of Monoalcohols.- 3.3 Lactones from Diols.- 3.4 Lactones from Lactols.- 3.5 Hydroxy Ketones from Diols. Cleavages of a-Diois.- 3.6 Steroids. Di- and Triterpenes.- 3.7 Carbohydrates.- 3.7.1 Regioselectivity.- 3.7.2 Degradation.- 3.8. Oxidation of Phenols.- 3.8.1 Formation of Quinones.- 3.8.2 Oxidative Coupling of Phenols.- 3.9 Aliphatic Amines.- 3.10 Aromatic Amines.- 3.11 Hydrazine Derivatives.- 3.12 Hydroxylamines.- 3.13 Oximes.- 3.14 Fragmentation Reactions.- 3.15 Rearrangements: Halohydrins.- 3.16 Miscellaneous Reactions.- 4. Experimental Procedures.- 4.1 Silver Carbonate on Celite Preparation.- 4.2 Recovery of Silver Nitrate.- 4.3 Oxidation of 2-(3-Cyclohexenyl)-1-Propanol.- 4.4 Oxidation of 4-Hydroxydendrolasin to (E)-9-(Furan-3’-yl)-2,6-Dimethynona-2,6-dien-4-one.- 4.5 Oxidation of 3-Methylpentane-l,3,5-triol to Mevalonolactone.- 4.6 Oxidation of 2,6-Dimethylphenol to 3,3’,5,5’-Tetramethyldiphenoquinone.- 4.7. Oxidation of Benzaidehyde Oxime to 3,5-Diphenyl-l,2,4-Oxadiazole.- References.- 11. Cerium(IV) Oxidation of Organic Compounds.- 1. Introduction.- 2. Mechanism.- 2.1 General Considerations.- 2.2 C-H Bond Fission Reactions.- 2.3 C-C Bond Cleavage Reactions.- 2.4 1,5-Hydrogen Transfer.- 2.5 Oxidation of Aromatic Compounds.- 2.6 Additive Oxidation.- 2.7 Miscellaneous.- 3. Scope and Limitations.- 3.1 General Aspects.- 3.2 Alcohols.- 3.3 Carbonyl Compounds and Derivatives.- 3.3.1 Aldehydes.- 3.3.2 Cyclic Ketones.- 3.3.3 ?-Keto Esters and Stabilized Anions.- 3.3.4 Oximes and Semicarbazones.- 3.3.5 Nitronates.- 3.3.6 Carboxylic Acids and Derivatives.- 3.4 Amines.- 3.5 Organosulfur Compounds.- 3.6 Aromatic Compounds.- 3.6.1 Quinones from Phenol Derivatives and Polycyclic Arenes.- 3.6.2 Miscellaneous.- 3.7 Organometallics.- 3.8 Miscellaneous Topics.- Note Added in Proof.- 4. Experimental Conditions and Procedures.- 5. Tabular Survey of Oxidation Reactions.- References.- 12. Oxidations of Organic Compounds with Osmium Tetroxide.- 1. Introduction.- 1.1. Chemical Nature of Osmium Tetroxide.- 2. General Mechanism of Osmium Tetroxide Oxidation Reactions.- 3. Scope and Limitations.- 3.1. Oxidation of Alkenes and Related Compounds.- 3.1.1 Noncatalytic cw-Hydroxylation of Alkenes.- 3.1.2 Catalytic cis-Hydroxylation of Alkenes.- 3.1.2a. With Hydrogen Peroxide.- 3.1.2b. With Metal Chlorates.- 3.1.2c With tert-Butyl Hydroperoxide.- 3.1.2d. With N-Methylmorpholine N-Oxide.- 3.1.2e. With Sodium Periodate.- 3.1.2f. With Oxygen.- 3.1.2g. With Sodium Hypochlorite.- 3.1.3. Oxidation of Alkenes and Related Compounds by Alkylimido-osmium Compounds.- 3.1.4 Oxidation of Alkenes by Chloramine-T (Osmium Catalyzed).- 3.1.5 Oxidation of Alkenes by N-chloro-N -argentocarbamates (Osmium Catalyzed).- 3.2 Oxidation of Alkynes (Acetylenes).- 3.3 Oxidation of Dienes.- 3.4 Oxidation of Quinones.- 3.5 Oxidation of Steroids.- 3.6 Oxidation of Pyrans.- 3.7 Oxidation of Alcohols and Related Compounds.- 3.8 Oxidation of Diols and Related Compounds.- 3.9 Oxidation of Aldehydes and Ketones.- 3.10 Oxidation of Hydroxy Acids.- 3.10.1 Oxidation of Glycolic and Lactic Acids.- 3.10.2 Oxidation of Malic and Mandelic Acids.- 3.10.3 Oxidation of Tartaric Acid.- 3.11.Oxidation of Dicarboxylic Acids.- 3.11.1 Maleic and Fumaric Acid.- 3.11.2 Oxidation of Malonic Acid.- 3.12. Osmium Tetroxide in the Biochemistry Field.- 4. Experimental Considerations and Procedures.- 4.1 Osmium Tetroxide in Alkaline Medium.- 4.2 Oxidation of Alkenes by Criegee’s Method.- 4.2.1 In the Absence of Bases.- 4.2.2 In the Presence of Bases.- 4.3 General Procedure for the Cleavage of Osmate-Esters.- 4.4 OsO4-Catalyzed cis-Hydroxylation of Alkenes.- 4.4.1 Oxidation of Cyclohexene with Os04/H20:.- 4.4.2 Oxidation with Os04/Metal Chlorates.- 4.4.2a. Oxidation of Crotonic Acid to Dihydroxybutyric Acid by Osmic Acid/Barium Chlorate.- 4.4.2b. Oxidation of Crotonic Acid with Os04/Potassium Chlorate.- 4.4.2c. Oxidation of Crotonic Acid with Osmic Acid/Silver Chlorate.- 4.4.2d. Oxidation by Gradual Addition of Silver Chlorate.- 4.4.3 Oxidation of Octene to Threo-4,5-dihydroxy Octane with Os04/Tert-Butyl Hydroperoxide.- 4.4.4 Oxidation of Cyclohexene to cis-cyclohexane-l,2-diol with Os04/N-Methyl Morpholine /N -Oxide.- 4.4.5 Oxidation of Cyclohexene to Adipaldehyde with Os04/Sodium Periodate.- 4.5. Oxidation of Alkenes by Imido Reagent.- 4.5.1 Preparation of Tert-Butyl Imido/Osmium Reagent.- 4.5.2 Oxyamination of Olefins—General Procedure.- 4.5.2a. Bi-sulfite Method.- 4.5.2b. Lithium Aluminum Hydride Method.- 4.6. Oxidation of Alkenes by Os04/ChIoramine-T.- 4.6.1 Phase Transfer Method.- 4.6.2 Tert/-Butyl Alcohol Method.- 4.7 Oxidation of Alkenes by Os04/N-chloro-N-argento Carbamates.- 4.8 Oxidation Alkynes.- 4.8.1. Preparation of Osmium Tetroxide-Amine Adducts.- 4.8.1a. Osmium(VI) Esters from Alkynes.- 4.8.1b. Hydrolysis of the Complex Os2O4(O4Cl4HI0)(NC5H5)4 to Benzil.- 4.8.2. Catalytic Oxidation of Diphenylacetylene.- 4.9. Oxidation of Dienes.- 4.9.1. Preparation of OsO4/Pyridine Complexes Os2O4(O4R)L4.- 4.10 Oxidation of Quinones.- 4.11 Oxidation of Steroids.- 4.12 Oxidation of Pyrane.- 4.13 Synthesis of ?-Keto Aldehyde from a?,?-Unsaturated Ketone.- 4.14 Synthesis of Methyl-7-(2-hydroxy-5-oxo-l-pyroridinyl) Heptonoate.- 4.15 Synthesis of (l’Rs, 2’Rs)-8-oxo-3 endo-(1’, 2’-dihydroxyheptyl)tricyclo-4.3.0.0 nonane.- 4.16. Synthesis of ‘K-Region’ Diepoxide.- References.- 13. Thallium(IH) Salts as Oxidants in Organic Synthesis.- 1. Introduction.- 2. Scope and Limitations.- 2.1. One-Electron Transfer Reactions.- 2.1.1 Dehydrodimerization of Aromatic Compounds.- 2.1.2 Intramolecular Cyclizations.- 2.1.3 Oxidation of Porphyrins.- 2.2. Two-Electron Transfer Reactions.- 2.2.1 Oxythallation Reactions, General Features.- 2.2.2 Oxythallation of Double and Triple Bonds.- 2.2.3 Oxidation of Nitrogen Compounds.- 2.2.4 Oxidation of Organosulfur Compounds.- 2.3. Reactions of Uncertain Mechanisms. Oxidation of Phenols and Derivatives.- 3. Experimental Considerations and Procedures.- References.- 14. Oxidations with Lead Tetraacetate.- 1. Introduction.- 2. Hydrocarbons.- 2.1. Saturated Hydrocarbons.- 2.1.1 Mechanism.- 2.1.2 Scope and Limitations.- 2.2. Unsaturated Hydrocarbons.- 2.2.1 Mechanism.- 2.2.2 Scope and Limitations.- 2.2.2a. Acyclic Olefins.- 2.2.2b. Cyclic Olefins.- 2.2.2c. Polycyclic Olefins and Terpenes.- 2.2.2d. Dienes and Polyenes.- 2.2.2e. Allenes and Acetylenes.- 2.3. Aromatic Hydrocarbons.- 2.3.1 Mechanism.- 2.3.2 Scope and Limitations.- 2.3.2a. Aromatic Rings.- 2.3.2b. Benzylic Groups.- 2.4. Vinyl Ethers and Enamines.- 3. Monohydroxylic Alcohols.- 3.1. Intramolecular Cyclization to Cyclic Ethers.- 3.1.1. Saturated Alcohols.- 3.1.1a. Mechanism.- 3.1.1b. Scope and Limitations.- 3.1.2. Unsaturated Alcohols.- 3.1.2a. Mechanism.- 3.1.2b. Scope and Limitations.- 3.2. ?-Fragmentation.- 3.2.1 Mechanism.- 3.2.3 Scope and Limitations.- 3.3. Oxidation to Carbonyl Compounds.- 3.3.1 Mechanism.- 3.3.2 Scope and Limitations.- 4. 1,2-Diols and Polyols.- 4.1 Mechanism.- 4.2 Scope and Limitations.- 5. Phenols.- 5.1 Mechanism.- 5.2 Scope and Limitations.- 6. Carbonyl Compounds.- 6.1 Mechanism.- 6.2 Scope and Limitations.- 7. Carboxylic Acids.- 7.1 Mechanism.- 7.2 Scope and Limitations.- 8. Nitrogen-Containing Compounds.- 8.1 Amines.- 8.2 Amides.- 8.3 Hydrazines.- 8.4 Oximes.- 8.5 Hydrazones.- 9. Experimental Considerations and Procedures.- 9.1 Hydrocarbons.- 9.2 Monohydroxylic Alcohols.- 9.3 1,2-Diols and Polyols.- 9.4 Phenols.- 9.5 Carbonyl Compounds.- 9.6 Carboxylic Acids.- 9.7 Nitrogen-Containing Compounds.- 10. Addendum.- 10.1 Hydroperoxides.- 10.2 Olefinic Dicarboxylic Acids.- References.- 15. Bismuth-Salt Oxidations.- 1. Introduction.- 2. Sodium Bismuthate Oxidations.- 2.1. Mechanism and Scope.- 2.2. Experimental Considerations and Procedures.- 2.2.1 Availability of the Reagent.- 2.2.2 1,2-Diol and Related Oxidations.- 2.2.3 Oxidation of Phenols.- 2.2.4 Oxidation of Olefins.- 3. Bismuth Trioxide Oxidations.- 3.1 Mechanism and Scope.- 3.2 Experimental Considerations and Procedures.- 4. Organobismuth Reagents.- 4.1 Mechanism and Scope.- 4.2 Experimental Considerations and Procedures.- 4.2.1 Preparation of the Reagents.- 4.2.2 Oxidation with Organobismuth Reagents.- 5.The Toxicity of Bismuth.- References.- 16. Oxidations with Metal Compounds and Peroxides.- 1. Introduction.- 2. Mechanism.- 2.1. Radical Mechanism via Redox Reactions (Category a).- 2.1.1 H Abstraction.- 2.1.2 Aromatic and Other Substitution Reactions.- 2.1.3 Addition to Double and Triple Bonds.- 2.2. Ionic Mechanism via Formation of Metallic Peroxide or Metal-PeroxideComplexes (Category b).- 2.2.1 Epoxidations.- 2.2.2 Oxygenation of Sulfides and Sulfoxides.- 2.2.3 Oxygenation of Amines.- 2.2.4 Formation of Glycols.- 2.3. Ionic Mechanism via Lewis Acid Activation.- 3. Scope and Limitations.- 3.1 General Considerations.- 3.2 Oxidation of Alcohols.- 3.2.1 Alcohols.- 3.2.2 Cleavage of Glycols and Related Compounds.- 3.3. Oxidation of Carbonyl Compounds.- 3.3.1 Aldehydes.- 3.3.2 Ketones.- 3.4. Oxidation of Double Bonds.- 3.4.1 Epoxidation of Olefins.- 3.4.2 Regio-and Stereoselective Epoxidations.- 3.4.3 Dihydroxylation of Olefins.- 3.4.4 Oxidative Cleavage.- 3.4.5 Ketones from Terminal Olefins.- 3.4.6 Oxidation of C = N Bonds.- 3.5. Oxidation of C-H Bonds.- 3.5.1 Direct Hydroxylation of Aliphatic C-H Bonds.- 3.5.2 Oxidation of Ethers.- 3.5.3 Oxidation of Benzylic C-H Bonds.- 3.5.4 Direct Hydroxylation of Aromatic Rings.- 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 Availability 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.