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.

Contenu

1. Oxidation by Vanadium Compounds.- 1. Introduction.- 2. Mechanisms.- 3.Scope and Limitations.- 4.Experimental Considerations and Procedures.- References.- 2. Oxidation by Oxochromium(VI) Compounds.- 1. Introduction.- 2. Mechanisms.- 3.Scope and Limitations.- 4.Experimental Considerations and Procedures.- References.- 3. The Oxidation of Organic Compounds by Active Manganese Dioxide.- 1.Introduction.- 2.Mechanism.- 3.Oxidation of Alcohols and Hydroxy Compounds.- 4.Dehydrogenation and Oxidative Aromatization.- 5.Hydrocarbons.- 6.Amines and Hydrazines.- 7.Miscellaneous Oxidations.- 8.Experimental Procedures.- References.- 4. Reactions with Manganese(III) Acetate.- 1. Introduction.- 2. Synthesis and Properties of Manganese (III) Acetate.- 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.- 6. Mn(III) Acetate-Acetone - Initiated Addition of Haloalkanes to Unsaturated Systems.- 7. Aromatic Substitution Reactions.- 8. Direct Oxidation Reactions with Manganese (III) Acetate.- 9. Synthetic Procedures.- References.- 5. Oxidations by Cobalt Compounds.- 1. Introduction.- 2. Mechanisms.- 3. Scope and Limitations.- 4. Experimental Considerations and Procedures.- References.- 6. Oxidation of Organic Compounds with Nickel Peroxide.- 1. Introduction.- 2. Mechanism of Oxidation.- 3. Scope and Limitations.- 4. Experimental Considerations.- References.- 7. Oxidations of Organic Compounds Catalyzed by Copper- and Cobalt-Amine Complexes.- 1. Introduction.- 2. Mechanism.- 3. Scope and Limitations.- 4. Experimental Considerations and Procedures.- 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.- 3. Scope and Limitations.- 4. Experimental Considerations and Procedures.- References.- 9. Oxidations Using Palladium Compounds.- 1. Introduction.- 2. Oxidation of Olefins.- 3. Vinylic Substitution Reactions.- 4. Aromatic Substitution Reactions.- 5. Oxidative Carbonylations.- 6. Some Reactions of Alcohols.- 7. Examples.- References.- 10. Silver Carbonate on Celite Oxidations.- 1. Introduction.- 2. Mechanism.- 3. Scope and Limitations.- 4. Experimental Procedures.- References.- 11. Cerium(IV) Oxidation of Organic Compounds.- 1. Introduction.- 2. Mechanism.- 3. Scope and Limitations.- 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.- 2. General Mechanism of Osmium Tetroxide Oxidation Reactions.- 3. Scope and Limitations.- 4. Experimental Considerations and Procedures.- References.- 13. Thallium(IH) Salts as Oxidants in Organic Synthesis.- 1. Introduction.- 2. Scope and Limitations.- 3. Experimental Considerations and Procedures.- References.- 14. Oxidations with Lead Tetraacetate.- 1. Introduction.- 2. Hydrocarbons.- 3. Monohydroxylic Alcohols.- 4. 1,2-Diols and Polyols.- 5. Phenols.- 6. Carbonyl Compounds.- 7. Carboxylic Acids.- 8. Nitrogen-Containing Compounds.- 9. Experimental Considerations and Procedures.- 10. Addendum.- References.- 15. Bismuth-Salt Oxidations.- 1. Introduction.- 2. Sodium Bismuthate Oxidations.- 3. Bismuth Trioxide Oxidations.- 4. Organobismuth Reagents.- 5.The Toxicity of Bismuth.- References.- 16. Oxidations with Metal Compounds and Peroxides.- 1. Introduction.- 2. Mechanism.- 3. Scope and Limitations.- 4. Experimental Considerations and Procedures.- References.