Comprehensive organic reactions in aqueous media

Cover Page......Page 1
Title Page......Page 6
ISBN 047176129X......Page 7
CONTENTS......Page 10
PREFACE TO THE SECOND EDITION......Page 18
1 INTRODUCTION......Page 20
1.1 The Structure and Forms of Water......Page 22
1.2 Properties of Water......Page 23
1.4 Hydrophobic Effect......Page 25
1.5 Salt Effect......Page 27
1.6 Water Under Extreme Conditions......Page 28
References......Page 32
2.1 Oxygenation of Alkanes......Page 34
2.3 Formation of Carbon–Carbon Bonds......Page 39
2.4 D/H Exchange of Alkanes in Water......Page 40
References......Page 41
3.1.1 Hydrogenation......Page 44
3.2.2 Reaction with Hydrogen Halides......Page 47
3.2.4 Oxymercuration/Oxymetalation......Page 48
3.2.5 Epoxidation......Page 49
3.2.6 Dihydroxylation and Hydroxylamination......Page 54
3.2.7 Wacker’s Oxidation......Page 59
3.2.8 Oxidative C=C Bond Cleavage......Page 62
3.2.9 C–C Bond Formations......Page 65
3.3.1 Radical Polymerization of Alkenes......Page 66
3.3.2 Radical Additions......Page 67
3.3.3 Radical Cyclization......Page 68
3.4.2 The Stability of Carbenes......Page 69
3.4.3 The Reaction of Carbenes with Alkenes in Aqueous Medium......Page 70
3.5 Alkene Isomerization......Page 71
3.6.1 Polymerizations......Page 72
3.6.2 Heck Reactions and Related Vinylation/Arylation......Page 73
3.6.4 Reaction with Arenes......Page 75
3.6.5 Hydroformylation......Page 76
3.6.6 Reaction with Alkynes......Page 77
3.7 Olefin Metathesis......Page 79
3.7.1 Ring-Opening Metathesis Polymerization (ROMP)......Page 80
3.7.2 Ring-Closing Metathesis (RCM)......Page 81
3.8.1 Allylic Oxidation......Page 83
3.8.2 C–C Bond Formations......Page 84
References......Page 85
4.1.1 Alkyne Oxidative Dimerization......Page 96
4.1.2 Alkyne-Alkyne Addition......Page 97
4.1.3 Reaction of Alkynes with Organic Halides......Page 100
4.1.4 Reaction of Alkynes with Carbonyl Compounds......Page 112
4.1.5 Reaction of Alkynes with C=N Compounds......Page 113
4.1.6 Conjugate Addition with Terminal Alkynes......Page 116
4.2.2 Addition of Water......Page 117
4.2.3 Addition of Alcohols and Amines......Page 119
4.2.4 Hydrosilation and Hydrometalations......Page 121
4.2.5 Addition of Aryls......Page 123
4.2.6 Carbonylation of Internal Alkynes......Page 126
4.3.1 Pauson-Khand-Type Reactions......Page 128
4.3.2 [2 + 2 + 2] Cyclotrimerization......Page 130
4.3.4 [3 + 2] 1,3-Dipolar Cycloaddition......Page 133
4.3.5 [4 + 2] Cycloaddition......Page 137
4.3.7 Other Cycloadditions......Page 138
References......Page 140
5.1 Oxidation of Alcohols......Page 148
5.2 Substitutions/Elimination......Page 153
5.4 Addition of Alcohols to C=O Bonds: Esterification and Acetal Formations......Page 156
5.5.1 Ethers and Cyclic Ethers......Page 157
5.5.2 Reactions of Epoxides in Water and “Click Chemistry”......Page 158
5.6.1 Oxidation of Thiols and Thioethers......Page 160
5.6.2 Reduction of Disulfides......Page 161
5.6.4 Other Reactions......Page 162
References......Page 163
6.2 Reduction......Page 170
6.4.1 Substituted by Heteroatoms......Page 173
6.4.2 Carbon–Carbon Bond Formations......Page 177
6.5.1 Wurtz-Type Coupling......Page 180
6.5.2 Ullmann-Type Coupling and Related Reactions......Page 182
6.6.1 Carbonylation of Alkyl Halides......Page 183
6.6.3 Carbonylation of Aryl Halides......Page 184
6.7.1 The Heck Coupling......Page 185
6.7.2 The Suzuki Coupling......Page 186
6.7.3 The Stille Coupling......Page 191
6.7.4 Other Transition-Metal Catalyzed Couplings......Page 192
References......Page 193
7.1 General......Page 200
7.2.1 Electrophilic Substitutions......Page 201
7.2.2 Friedel-Crafts C–C Bond Formations......Page 202
7.2.3 Other Substitution Reactions......Page 208
7.3.1 Simple Oxidation......Page 209
7.3.2 Oxidative Coupling......Page 210
7.4 Reductions......Page 211
References......Page 212
8.1.1 Hydrogenation......Page 216
8.1.2 Other Reductions......Page 217
8.2 Oxidation......Page 223
8.3.1 Allylation......Page 225
8.3.2 Propargylation......Page 257
8.3.4 Benzylation......Page 261
8.3.5 Arylation/Vinylation......Page 263
8.3.8 Reformatsky-Type Reaction......Page 265
8.3.9 Direct Aldol Reaction......Page 267
8.3.10 Mukaiyama Aldol Reaction......Page 271
8.3.11 Hydrogen Cyanide Addition......Page 277
8.3.12 Wittig Reactions......Page 278
8.4 Pinacol Coupling......Page 280
8.5 Other Reactions (Halogenation and Oxidation of α-H)......Page 281
References......Page 282
9.1.2 Reduction......Page 298
9.2.1 Esterification/Amidation......Page 299
9.3.1 Esters and Thiol Esters......Page 306
9.3.2 Acid Halides and Anhydrides......Page 307
9.3.4 Nitriles......Page 308
References......Page 309
10.1.1 Hydrogenation......Page 312
10.1.2 Asymmetric Hydrogenation......Page 314
10.1.3 Reduction by Other Methods......Page 315
10.2 Epoxidation, Dihydroxylation, Hydroxyamination......Page 316
10.3 Conjugate Addition: Heteroatom......Page 317
10.4 C–C Bond Formation......Page 320
10.4.2 Addition of α-Carbonyl Compounds......Page 321
10.4.3 Addition of Allyl Groups......Page 323
10.4.4 Addition of Alkyl Groups......Page 324
10.4.5 Addition of Vinyl and Aryl Groups......Page 326
10.5.1 Reductive Coupling......Page 329
10.5.2 Baylis-Hillman Reactions......Page 330
10.5.3 γ-Addition of Alkynoates......Page 333
References......Page 334
11.1.1 Alkylation......Page 340
11.1.2 Diazotization and Nitrosation......Page 341
11.1.3 Oxidation......Page 342
11.1.4 Reaction with Carbonyl Compounds......Page 345
11.2.1 Reductions......Page 346
11.2.2 Nucleophilic Additions......Page 348
11.2.3 Reductive Coupling......Page 361
11.3.2 Reduction......Page 362
11.3.3 Cyclopropanation......Page 363
11.4.1 Substitution......Page 365
11.4.2 Click Chemistry......Page 366
References......Page 368
12.1 Introduction......Page 374
12.2 Diels-Alder Reactions......Page 376
12.2.1 Lewis-Acid Catalysis......Page 379
12.2.2 Asymmetric Diels-Alder Reactions......Page 386
12.2.3 Theoretical and Mechanistic Studies......Page 390
12.2.4 Synthetic Applications......Page 393
12.2.5 Hetero-Diels-Alder Reactions......Page 401
12.2.6 Asymmetric Hetero-Diels-Alder Reactions......Page 407
12.2.7 Other Cyclization Reactions......Page 409
12.3.1 Claisen Rearrangements......Page 411
12.3.2 Cope Rearrangements......Page 416
12.4 Photochemical Cycloaddition Reactions......Page 417
References......Page 418
INDEX......Page 428