Metal-Catalyzed Oxidations of Organic Compounds - 1st Edition - ISBN: 9780126393804, 9780323150040

Metal-Catalyzed Oxidations of Organic Compounds

1st Edition

Mechanistic Principles and Synthetic Methodology Including Biochemical Processes

Authors: Roger Sheldon
eBook ISBN: 9780323150040
Imprint: Academic Press
Published Date: 28th October 1981
Page Count: 446
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Metal-Catalyzed Oxidations of Organic Compounds: Mechanistic Principles and Synthetic focuses on the oxidative transformations of functional groups. This book explores oxidation as being extensively used in the laboratory synthesis of fine organic chemicals and in the manufacture of large-volume petrochemicals. Organized into two parts encompassing 13 chapters, this book starts with an overview of the mechanistic principles of oxidation–reduction in biochemical, organic, and inorganic systems. This text then proceeds with a discussion of the use of molecular oxygen, hydrogen peroxide, and alkyl hydroperoxides as primary oxidants. Other chapters explore stoichiometric oxidations with metal oxidants, which include permanganate and chromic acid. This book discusses as well the synthetic applications of catalytic oxidations as well as the technology of petrochemical oxidation. The final chapter deals with the autoxidations of sulfur, phosphorus, and nitrogen compounds.
This book is intended for chemists involved in organic synthesis, catalysis, and organometallic chemistry, both in academic institutions and in industrial laboratories.

Table of Contents




Chapter 1 Introduction to Metal-Catalyzed Oxidations

I. Historical Development

II. Sources of Hydrocarbons

III. Definition of Oxidation

IV. Mechanistic Principles of Metal-Catalyzed Oxidation

V. Homogeneous and Heterogeneous Catalysis

VI. Biochemical Oxidations

VII. Synthetic Methodology for Organic Oxidations


Additional Reading

Part One Mechanistic Principles of Metal-Catalyzed Oxidations

Chapter 2 Oxidations with Molecular Oxygen

I. Fundamentals of Radical-Chain Processes

II. Aldehyde Autoxidation

III. Olefin Autoxidation

IV. Cooxidations

V. Gas-Phase versus Liquid-Phase Processes

VI. Inhibition of Autoxidations

VII. Solvent Effects


Additional Reading

Chapter 3 Metal Catalysis in Peroxide Reactions

I. Homolytic Catalysis

II. Heterolytic Catalysis


Additional Reading

Chapter 4 Activation of Molecular Oxygen by Metal Complexes

I. Oxygen Fixation: Historical Development

II. Peroxometal Complexes: Structural Types

III. Nucleophilic Peroxometal Complexes

IV. Electrophilic Peroxometal Complexes

V. Superoxo- and ì-Peroxometal Complexes

VI. Oxygen Transfer from Coordinated Ligands


Additional Reading

Chapter 5 Direct Homolytic Oxidation by Metal Complexes

I. Aromatic Compounds

II. Alkenes

III. Alkanes

IV. Carbonyl Compounds

V. Alcohols and Glycols

VI. Electrochemical Generation of Metal Oxidants


Additional Reading

Chapter 6 Direct Oxidation by Oxometal (M=0) Reagents

I. Oxometal Reagents: Mechanistic Formulations

II. Allylic Oxidations

III. Oxidation at the Carbon-Carbon Double Bond

IV. Allylic Oxidation versus Double Bond Attack

V. Oxoiron Species in Enzymatic Hydroxylation and Epoxidation

VI. Oxidations of Alcohols

VII. Phase-Transfer Catalysis in Oxidations with Oxometal Reagents


Additional Reading

Chapter 7 Activation by Coordination to Transition Metal Complexes

I. Palladium-Catalyzed Oxidations of Olefins in Aqueous Media

II. Palladium-Catalyzed Oxidations of Olefins in Nonaqueous Media

III. Oxidative Carbonylation of Olefins

IV. Oxidation of Aromatic Compounds by Palladium(II) Complexes

V. Oxidation of Alcohols to Carbonyl Compounds

VI. Palladium(II)-Catalyzed Oxidations with Hydroperoxides

VII. Activation of Alkanes by Metal Complexes


Additional Reading

Chapter 8 Biochemical Oxidations

I. Terminology

II. Coenzymes and Prosthetic Groups

III. Types of Oxidative Transformation

IV. Mechanisms of Enzymatic Oxidation

V. Biomimetic Oxygénations

VI. Immobilized Enzymes


Additional Reading

Part Two Synthetic Methodology for Metal-Catalyzed Oxidations

Chapter 9 Olefins

I. Autoxidation

II. Epoxidation

III. Allylic Oxidation

IV. Glycol (Ester) Formation

V. Oxidative Cleavage

VI. Oxidative Ketonization

VII. Oxidative Nucleophilic Substitution

VIII. Oxidative Carbonylation

IX. Oxidative Dimerization

X. Conjugated Dienes

XI. Acetylenes


Chapter 10 Aromatic Hydrocarbons

I. Autoxidation

II. Metal-Catalyzed Autoxidations of Alkylbenzenes to Carboxylic Acids

III. Metal-Catalyzed Autoxidations of Alkylbenzenes to Aldehydes and Ketones

IV. Metal-Catalyzed Oxidations of Alkylbenzenes to Benzylic Acetates

V. Oxidative Nuclear Substitution

VI. Oxidative Dimerization

VII. Oxidative Cleavage


Chapter 11 Alkanes

I. Formation of Alkyl Hydroperoxide

II. Alcohol and Ketone from Alkane

III. Carboxylic Acid Formation


Chapter 12 Oxygen-Containing Compounds

I. Alcohols

II. Ethers

III. Glycols

IV. Aldehydes

V. Ketones

VI. Phenols


Chapter 13 Nitrogen, Sulfur, and Phosphorus Compounds

I. Nitrogen Compounds

II. Sulfur Compounds

III. Phosphorus Compounds


Additional Reading



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About the Author

Roger Sheldon

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