Metal-Catalyzed Oxidations of Organic Compounds

Metal-Catalyzed Oxidations of Organic Compounds

Mechanistic Principles and Synthetic Methodology Including Biochemical Processes

1st Edition - October 28, 1981

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  • Author: Roger Sheldon
  • eBook ISBN: 9780323150040

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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

  • Preface



    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


Product details

  • No. of pages: 446
  • Language: English
  • Copyright: © Academic Press 1981
  • Published: October 28, 1981
  • Imprint: Academic Press
  • eBook ISBN: 9780323150040

About the Author

Roger Sheldon

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