Organic Syntheses by Oxidation with Metal Compounds

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.

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 Cata...