<strong>CONTENTS</strong>
Glossary, xi
Abbreviations, xiii
<strong>1. PRACTICAL BACKGROUND 1</strong>
1-1. Electrode Potential, 1
1-2. Standard and Formal Electrode Potentials; The Nernst Equation, 2
1-3. Electrode Kinetics, 6
1-4. The Electrical Double Layer and Adsorption, 13
1-5. Cyclic Voltammetry, 16
1-6. Controlled-Potential Electroreaction and Coulometry, 25
1-6-1.&
;nbsp; Controlled-Potential Electroreaction, 25
1-6-2.&
;nbsp; Coulometry at Controlled Potential, 29
1-7. Experimental Arrangements, 30
1-7-1.&
;nbsp; Cells and Electrodes, 30
1-7-2.&
;nbsp; Reference Electrodes, 31
1-7-3.&
;nbsp; Solvent and Supporting Electrolyte, 32
References
, 34
<strong>2. FORMATION AND TRANSFORMATION OF CATION
RADICALS 37</strong>
2-1. Cationic Species as Synthetic Intermediates, 37
2-2. Possible Intermediates; Monocation Radicals and Dications, 43
2-2-1.&
;nbsp; Oxidation Potentials of Reactants, 37
2-2-2.&
;nbsp; Electrogeneration and Investigation of Cation Radicals and Dications, 44
2-2-3.&
;nbsp; Disproportionation of Cation Radicals, 61
2-3. ECE Products, 65
References
, 68
<strong>3. REACTION BETWEEN STABLE CATION RADICALS AND
NUCLEOPHILES 73</strong>
3-1. Reaction With Aromatics, 73
3-1-1.&
;nbsp; Homogeneous Electron-Transfer Reaction, 73
3-1-2.&
;nbsp; Dimerization, 76
3-2. Reaction With Water, 79
3-3. Reaction With Amines, 83
3-4. Reaction With Halide Ions, 87
3-5. Reaction With Cyanide Ion, 90
3-6. Reaction With Other Nucleophiles, 92
3-7. Relative Reactivities of Nucleophiles Toward Cation Radicals, 94
References
, 95
<strong>4. CARBON–CARBON BOND
FORMATION 99</strong>
4-1. Anodic Cyanation, 99
4-1-1.&
;nbsp; Heterocyclic Aromatic Compounds, 100
4-1-2.&
;nbsp; Phenol Ethers, 109
4-1-3.&
;nbsp; Homocyclic Methyl Aromatic Compounds, 112
4-1-4.&
;nbsp; Aromatic and Aliphatic Amines, 117
4-1-5.&
;nbsp; Diaryl Acetylenes and Olefins, 119
4-1-6.&
;nbsp; Miscellaneous Aromatic Compounds, 120
4-1-7.&
;nbsp; Use of MO Theory to Predict Positional Reactivity, 121
4-2. Intermolecular Coupling, 126
4-2-1.&
;nbsp; Ring–Ring Coupling, 126
4-2-2.&
;nbsp; Coupling of Olefins, 136
4-3. Intramolecular Cyclization, 136
4-3-1.&
;nbsp; Aryl Olefins and Acrylamines, 136
4-3-2.&
;nbsp; Diaryl Alkanes and Cyclophanes, 137
4-3-3.&
;nbsp; 1-Aralkylisoquinoline Alkaloids and Related Compounds, 144
References
, 151
<strong>5. CARBON–OXYGEN BOND
FORMATION 156</strong>
5-1. Anodic Acyloxylation, 156
5-1-1.&
;nbsp; Aromatic Nuclear Substitution and Addition, 157
5-1-2.&
;nbsp; Alkyl Aromatics—Nuclear Versus Side-Chain Substitution, 162
5-1-3.&
;nbsp; <em>N</em>-Methylamides and β-Keto Sulfides, 165
5-1-4.&
;nbsp; Olefins, Dienes, and Acetylenes, 166
5-1-5.&
;nbsp; Intramolecular Acyloxylation, 173
5-2. Anodic Alkoxylation, 174
5-2-1.&
;nbsp; Furans, Phenol Ethers, and Phenols—Anodic Addition of an Alkoxy Group, 175
5-2-2.&
;nbsp; Ethers and Alcohols, 186
5-2-3.&
;nbsp; Amines and Amides, 189
5-2-4.&
;nbsp; Olefins, Dienes, and Cyclopropanes, 194
5-2-5.&
;nbsp; Unsubstituted Aromatic Hydrocarbons and Alkyl Aromatic Compounds, 200
5-2-6.&
;nbsp; Intramolecular Alkoxylation, 201
5-3. Anodic Hydroxylation, 202
5-3-1.&
;nbsp; Hydroxylation in Aqueous Systems, 202
5-3-2.&
;nbsp; Monohydroxylation by Way of Initial Trifluoroacetoxylation, 207
5-4. Anodic Aryloxylation, 212
References
, 212
<strong>6. CARBON–NITROGEN BOND
FORMATION 219</strong>
6-1. Anodic Acetamidation, 219
6-1-1.&
;nbsp; Methylbenzenes, 220
6-1-2.&
;nbsp; Alkyl Halides, 222
6-1-3.&
;nbsp; Saturated Hydrocarbons, 226
6-1-4.&
;nbsp; Aldehydes and Ketones, 228
6-1-5.&
;nbsp; Ethers and Esters, 233
6-1-6.&
;nbsp; Aromatic Acetamidation, 233
6-1-7.&
;nbsp; Olefins, Allenes, and Heterocumulenes, 235
6-2. Anodic Quaternization, 236
6-2-1.&
;nbsp; Aromatic Compounds, 238
6-2-2.&
;nbsp; Olefinic Compounds, 240
6-2-3.&
;nbsp; Intramolecular Quaternization, 241
6-3. Anodic Amination, 242
References
, 244
<strong>7. MISCELLANEOUS FUNCTIONALIZATION
REACTIONS 247</strong>
7-1. Acylation, 247
7-2. Carboxylation, 250
7-3. Friedel-Crafts Transalkylation, 251
7-4. Halofunctionalization, 252
7-4-1.&
;nbsp; Fluorination, 252
7-4-2.&
;nbsp; Chlorination and Bromination, 257
7-5. Introduction of an Isocyanato Group, 258
7-6. Nitration, 259
7-7. Oxygenation, 260
7-8. C—C Bond Formation, 262
7-9. C—N Bond Formation, 262
7-10. Electrochemical Removal of Protective Groups, 264
References
, 266
<strong>8. CATALYTIC ELECTRON-TRANSFER
REACTIONS 269</strong>
8-1. Electron-Transfer Chain (ETC) Reaction, 269
8-2. <em>In Situ</em> Circular Use of Cation-Radical Oxidants, 270
References
, 273
Author Index 275
Subject Index 287
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