Ketenes 2e

THOMAS T. TIDWELL, PhD, is a Professor of Chemistry at the University of Toronto.

Preface. Introduction. 1. STRUCTURE, BONDING, AND THERMOCHEMISTRY OF KETENES. 1.1 Theoretical Studies of Ketenes. 1.1.1 Molecular and Electronic Structure and Energy. 1.1.2 Theoretical Studies of Ketene Reactions. 1.1.3 Substituent Effects on Ketenes. 1.2 Molecular Structure Determinations. 1.3 Thermochemistry of Ketenes. 2. SPECTROSCOPY AND PHYSICAL PROPERTIES OF KETENES. 2.1 Nuclear Magnetic Resonance Spectroscopy. 2.2 Ultraviolet and Photoelectron Spectroscopy. 2.3 Infrared Spectra. 2.4 Dipole Moments. 2.5 Mass Spectrometry and Gas Phase Ion Chemistry. 3. PREPARATION OF KETENES. Ketenes from Ketene Dimers. 3.1 Ketenes from Carboxylic Acids and Their Derivatives. 3.1.1 Ketenes from Carboxylic Anhydrides. 3.1.2 Ketenes from Acyl Halides and Activated Acids. 3.1.3 Ketenes from Esters. 3.1.3.1 Ketenes from Ester Enolates. 3.1.3.2 Ketenes by Ester Pyrolysis. 3.1.3.3 Other Preparations of Ketenes from Esters. 3.1.4 Ketenes by Dehalogenation of ?-Halo Carboxylic Derivatives. 3.3 Ketenes from Diazo Ketones (Wolff Rearrangements). 3.3.1 Thermal Wolff Rearrangement. 3.3.2 Photochemical Wolff Rearrangement. 3.4 Ketenes by Photochemical and Thermolytic Methods. 3.4.1 Ketenes from Cyclobutanones and Cyclobutenones. 3.4.2 Ketenes from Photolysis of Cycloalkanones and Enones. 3.4.3 Ketenes from Cytclohexadienones and Other Cycloalkenones. 3.4.4 Ketenes from Dioxinones. 3.4.5 Ketenes by Thermolysis of Alkynyl Ethers. 3.4.6 Ketenes from Other Thermolytic and Photochemical Routes. 3.5 Ketenes from Alkenylcarbene Metal Complexes. 3.6 Ketene Formation under Acidic Conditions. 3.7 Ketenes from Oxidation of Alkynes. 3.8 Other Routes to Ketenes. 4. TYPES OF KETENES. 4.1 Carbon-Substituted Ketenes. 4.1.1 Alkylketenes. 4.1.2 Alkenylketenes. 4.1.3 Alkynylketenes and Cyanoketenes. 4.14 Arylketenes. 4.1.5 Cyclopropylketenes. 4.1.6 Acylketenes. 4.1.7 Imidoylketenes. 4.1.8 Cumulene-Substituted Ketenes. 4.1.9 Ketenes with Charged, Radical, or Carbenic Side Chains. 4.1.10 Fulvenones. 4.1.10.1 Triafulvenones. 4.1.10.2 Pentafulvenones. 4.1.10.3 Heptafulvenones. 4.1.10.4 Oxoquinone Methides and Related Species. 4.2 Nitrogen-Substituted Ketenes. 4.3 Oxygen-Substituted Ketenes. 4.4 Halogen-Substituted Ketenes. 4.4.1 Fluoroketenes, Perfluoroalkylketenes and Perfluoroarylketenes. 4.4.2 Chlorine, Bromine, and Iodine-Substituted Ketenes. 4.5 Silyl-, Germyl-, and Stannylketenes. 4.6 Phosphorous- and Arsenic-Substituted Ketenes. 4.7 Sulfur-Substituted Ketenes. 4.8 Metal-Substituted Ketenes. 4.8.1 Lithium Ketenes (Lithium Ynolates) and Ynols. 4.8.2 Boron-Substituted Ketenes. 4.8.3 Other Metal-Substituted Ketenes and Metal Ketenides. 4.8.4 Metal-Complexed Ketenes. 4.9 Bisketenes. 4.10 Ketenyl Radicals, Anions, and Cations. 4.11 Cumulenones. 5. REACTIONS OF KETENES. 5.1 Oxidation and Reduction of Ketenes (Electron Transfer). 5.2 Photochemical Reactions. 5.3 Thermolysis Reactions. 5.4 Cycloaddition Reactions of Ketenes. 5.4.1 Intermolecular [2+2] Cycloaddition. 5.4.1.1 Dimerization of Ketenes. 5.4.1.2 Cycloaddition with Alkenes and Dienes. 5.4.1.3 Mechanism of Ketene [2+2]. Cycloadditions with Alkenes. 5.4.1.4 Cycloaddition of Ketenes with Nucleophilic Alkenes. 5.4.1.5 Cycloaddition of Ketenes with Allenes. 5.4.1.6 Cycloaddition of Ketenes with Alkynes. 5.4.1.7 Cycloaddition of Ketenes with Imines. 5.4.1.8 Cycloadditions of Ketenes with Other Substrates. 5.4.2 [3+2] Cycloaddition Reactions of Ketenes. 5.4.3 [4+2] Cycloadditions of Ketenes. 5.4.4 Intramolecular Cycloadditions of Ketenes. 5.4.5 Intermolecular and Intramolecular Cycloaddition of Ketenes with Carbonyl Groups. 5.5 Nucleophilic Addition to Ketenes. 5.5.1 Mechanisms. 5.5.1.1 Theoretical Studies. 5.5.1.2 Kinetics of Hydration: Neutral and Base Reactions. 5.5.1.3 Acid-Catalyzed Hydration. 5.5.1.4 Alcoholysis and Aminolysis. 5.5.2 Nucleophilic Additions to Ketenes: Preparative Aspects. 5.5.2.1 Hydride Addition. 5.5.2.2 Oxygen Nucleophiles. 5.5.2.3 Nitrogen Nucleophiles. 5.5.2.4 Carbon Nucleophiles. 5.5.2.5 Other Nucleophiles. 5.5.3 Wittig Reactions. 5.6 Electrophilic Addition to Ketenes. 5.6.1 Protonation of Ketenes. 5.6.2 Electrophilic Addition of Hydrogen Halides to Ketenes. 5.6.3 Electrophilic Additions to Other Reagents. 5.6.4 Oxygenation of Ketenes. 5.7 Radical Reactions of Ketenes. 5.8 Polymerization of Ketenes. 5.9 Stereoselectivity in Ketene Reactions. 5.10 Other Additions to Ketenes. 5.10.1 Reaction with Diazomethanes. 5.10.2 Reaction with Sulfur Dioxide. 5.11 Ketene Reactions Using Polymer Supports. References. Index.