Although the first electroorganic reaction used in organic synthesis is probably the famous Kolbe electrolysis published in 1849, no other remarkable reactions have been found until the reductive dimerization of acrylonitrile to adipo­ nitrile was developed by Dr. M. M. Baizer of Monsanto Co. in 1964. Since then, the electro organic chemistry has been studied extensively with the expectation that it is a new useful tool for finding novel reactions in organic synthesis. The purpose of this book is not to give a comprehensive survey of studies on electrochemical reactions of organic compounds but to show that the electro organic chemistry is indeed useful in organic synthesis. Thus, this book has been written under the following policies. (1) Since this monograph is mainly concerned with organic synthesis, only few studies carried out from the view­ point of electrochemical, theoretical, or analytical chemistry are mentioned. (2) Since electroorganic chemistry covers a great variety of reactions, the types of reactions described in this book are selected mainly with regard to their application in organic synthesis. Simple transformations of functional groups are only described in particular cases, and also some well established processes such as the Kolbe electrolysis, pinacolic coupling, and hydrodimerization are only briefly mentioned. (3) Since many reports have already been published for each type of these reactions, only a limited number of the relevant papers are cited in this book.

Inhalt

1 Introduction.- 1.1 Inversion of Polarity of Substrates.- 1.2 Interface Reactions.- 1.2.1 Stereochemistry.- 1.2.2 Distribution of Active Species.- References.- 2 Anodic Oxidations.- 2.1 Anodic Cleavage of Aliphatic Carbon-Hydrogen Bonds and Carbon-Carbon Single Bonds.- 2.1.1 Cleavage of Carbon-Hydrogen Bonds.- 2.1.2 Cleavage of Carbon-Carbon Single Bonds.- References.- 2.2 Oxidation of Carbon-Carbon Double Bonds.- 2.2.1 Introduction.- 2.2.2 Oxidation of Simple Olefins.- 2.2.3 Oxidation of Conjugated and Nonconju- gated Dienes.- 2.2.4 Oxidation of Arylolefms.- 2.2.5 Oxidation of Enolic Olefins.- References.- 2.3 Oxidation of Alcohols, Glycols, Ethers, and Acetals.- 2.3.1 Oxidation of Alcohols.- 2.3.2 Oxidation of Glycols.- References.- 2.4 Oxidation of Compounds Containing Sulfur, Phosphorous, and Boron.- 2.4.1 Sulfur Compounds.- 2.4.2 Compounds Containing Phosphorous and Boron.- References.- 2.5 Oxidation of Organic Halides and Oxidative Halogenation of Organic Compounds.- 2.5.1 Oxidation of Organic Halides.- 2.5.2 Halogenation.- References.- 2.6 Oxidation of Aliphatic and Aromatic Amines.- 2.6.1 Oxidation of Aliphatic Amines.- 2.6.2 Oxidation of Aromatic Amines.- 2.6.3 Oxidation of Amides and Carbamates.- 2.6.4 Application of ?-Methoxy- or ?-Acetoxy- Amides or -Carbamates as Starting Materials in Organic Synthesis.- 2.6.4.1 Formation of Carbon-Carbon Bonds.- 2.6.4.2 Formation of Bonds between Carbon and Heteroatoms.- 2.6.4.3 Reactions Using ?-Methoxylated Amides and Carbamates as Masked Carbonyl Compounds.- 2.6.4.4 Formation of Enecarbamates and their Reactions.- References.- 2.7 Oxidation of Carbanions andCarboxylate Anions.- 2.7.1 Oxidation of Carbanions.- 2.7.2 Oxidation of Carboxylate Anions.- 2.7.2.1 Formation of Radicals Kolbe- Type Reactions.- 2.7.2.2 Formation of Cations.- References.- 2.8 Oxidation of Aromatic Systems.- 2.8.1 Aromatic Substitution.- 2.8.1.1 Acetoxylation.- 2.8.1.2 Methoxylation.- 2.8.1.3 Formation of Quinones.- 2.8.1.4 Miscellaneous Oxidations.- 2.8.1.5 Oxidation of Benzene.- 2.8.1.6 Acetamidation, Nitration, and Reactions with Pyridine.- 2.8.1.7 Halogenation.- 2.8.1.8 Cyanation.- 2.8.2 Coupling.- 2.8.2.1 Intramolecular Coupling.- 2.8.2.2 Intermolecular Coupling.- 2.8.3 Oxidation at the Benzylic Position.- 2.8.4 Oxidation of Furan, Pyrrole, and Thiophene.- 2.8.4.1 Furans.- 2.8.4.2 Pyrrole and Thiophene.- References.- 2.9 Oxidations Using Mediators.- 2.9.1 Principles.- 2.9.2 Homomediatory Systems.- 2.9.3 Heteromediatory Systems.- 2.9.4 Double Mediatory Systems.- References.- 3 Cathodic Reductions.- 3.1 Cathodic Addition, Substitution, and Coupling.- 3.1.1 Addition.- 3.1.2 Substitution.- 3.1.3 Coupling.- References.- 3.2 Cathodic Eliminations.- 3.2.1 1,1-Elimination.- 3.2.2 1,2-Elimination.- 3.2.3 1,3- and 1,4-Elimination.- 3.2.4 Deprotection.- References.- 3.3 Cathodic Generation of Active Bases.- 3.3.1 Reactions of Electrogenerated Bases.- References.- 1. Constant Current Oxidation.- 2. Controlled Potential Reduction.- 3. Indirect Oxidation Using a Mediator.