Electrochemical reactions make significant contributions to organic synthesis either in the laboratory or on an industrial scale. These methods have the potential for developing more "green" chemical synthesis. Over recent years, modern investigations have clarified the mechanisms of important organic electrochemical reactions. Progress has also been made in controlling the reactivity of intermediates through either radical or ionic pathways. Now is the time to gather all the electrochemical work into a textbook.
As an essential addition to the armory of synthetic organic chemists, electrochemical reactions give results not easily achieved by many other chemical routes. This book presents a logical development of reactions and mechanisms in organic electrochemistry at a level suited to research scientists and final year graduate students. It forms an excellent starting point from which synthetic organic chemists, in both academia and industry, can appreciate uses for electrochemical methods in their own work. The book is also a reference guide to the literature.
Synthetic organic chemists in academia and industry, electrochemists, research scientists and final year graduate chemistry students.
Electrochemical Reactions and Mechanisms in Organic Chemistry, 1st Edition
1. Electrochemical Oxidation and Reduction of Organic Compounds.
General Technique. Anode and Cathode Materials. Kinetics of Electron Transfer. Analytical and Spectroscopic Techniques. Pulse Radiolysis. 2. Oxidation of Alkanes, Haloalkanes and Alkenes.
Radical-Cations. Oxidation of Alkanes. Oxidation of Haloalkanes. Oxidation of Alkenes. Intramolecular Cyclization. Electrochemically Generated Reagents for Alkenes. 3. Alkenes and Conjugated Alkenes, Reduction.
Alkenes and Phenylalkenes. Alkene Radical-Anions as Nucleophiles. Activated Alkenes - Introduction. Activated Alkenes - Dimerization in Aprotic Media. Activated Alkenes - Dimerization in Protic Media. &agr;, &bgr;-Unsaturated Aldehydes and Ketones. Intramolecular Cyclization. Mixed Hydrocoupling Reactions. Asymmetric Reduction. Electrocatalytic Hydrogenation. 4. Reductive Bond Cleavage Processes - I.
Dissociative Electron Transfer. Reduction of Alkyl and Benzyl Halides. Reactions of the Trichloremethyl Group. Reductive Cyclization of &agr;, &ohgr;-Dihaloalkanes. Alkenes from 1,2-Dibromides and Related Compounds. Reduction of Aryl Halides. Electrochemically Induced SRN
1 Reaction. Electrochemically Induced Radical Cyclization Reactions of Aryl Halides. Carbon-Halogen Bond Reactions Catalysed by the Anode Material. Carbon-Halogen Bond Reactions Catalysed by Ni, Co and Pd Complexes. Reactions with Carbon Dioxide. 5. Reductive Bond Cleavage Processes - II.
Introduction. Carbon-Oxygen Bond Cleavage. Quaternary Ammonium Salts. Quaternary Phosphonium and Arsonium Salts. Carbon-Sulphur and Related Bond Cleavage. Cleavage Assisted by an Adjacent Carbonyl Function. Carbon-Carbon Bond Cleavage. The Abnormal Clemmensen Reaction. 6. Oxidation of Aromatic Rings.
Radical-Cations. Oxidative Substitution Reactions. Oxidation of Phenols. Intramolecular Cyclization Processes. Oxidation of Anilines. Oxidation of Aromatic Heterocycles. 7. Reduction of Aromatic Rings.
Aromatic Compounds Radical-Anions. Aromatic Hydrocarbons. Thiophene, Pyrrole and Indole Derivatives. Pyridine, Quinoline and Isoquinoline Derivatives. Other Nitrogen Heterocycles. Nitrogen-Nitrogen Bond cleavage. Reductive Alkylation and Carboxylation. Electrocatalytic Hydrogenation. 8. Alcohols, Amines and Amides, Oxidation.
Nitroxyl Radicals. Oxidation of Alcohols. Oxidation of Amines and Sulphonamides. Oxidation of Amides and Urethanes. Oxidation of Hydrazine Derivatives. 9. Aldehydes, Ketones and Carboxylic Acids, Oxidation.
Oxidation of Ketones. Oxidation of Aldehydes. Oxidation of Enolate Ions. Oxidation of Hydrazones and Oximes. Oxidation of Carboxylate - Introduction and Mechanism. The Kolbe Reaction. The Non-Kolbe Reaction. 10. Reduction of Carbonyl Compounds and their Derivatives.
Carbonyl Compounds Radical-anions. Aromatic Carbonyl Compounds - Mechanistic Studies. Aromatic Carbonyl Compounds - Enantiomeric Reduction. Aromatic Carbonyl Compounds - Carboxylation Reaction. Aliphatic Carbonyl Compounds. The Electrochemcial Clemmensen Reaction. Coupling with Unsaturated Functions. Reduction of Dicarbonyl Compounds. Reduction of &bgr;-Ketoesters - The Tafel Rearrangement. Carboxylic Acid Reduction. Esters and Lactones. Acid Amides. Acid Chlorides. Imines, Oximes and Hydrazones. Electrocatalytic Hydrogenation. 11. Reduction of Nitro, Nitroso, Axo and Azoxy Groups.
Nitro- and Nitroso-compounds Radical-Anions. Aliphatic Nitrocompounds. Formation of Arylamines. Formation of Nitrosoarenes and Arylhydroxylamines. Rearrangement of Phenylhydroxylamines - Formation of 4-Aminophenols. Formation of Heterocyclic Rings. Azoxybenzenes, Azobenzenes and Hydrazobenzenes. Nitramines and Nitrosamines. Benzenediazonium Salts.