Organic Syntheses by Oxidation with Metal Compounds

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.