Handbook of Synthetic Photochemistry

Handbook of Synthetic Photochemistry......Page 2
Foreword......Page 8
Contents......Page 10
Preface......Page 18
List of Contributors......Page 20
1.1.1 Photochemistry and Organic Synthesis......Page 24
1.2.1 General......Page 25
1.2.2 Low-Pressure Mercury Arcs......Page 26
1.2.3 Medium- and High-Pressure Mercury Arcs......Page 30
1.2.4 Other Light Sources......Page 32
1.3.1 Concentration and Scale......Page 34
1.3.2 Effect of Impurities, Oxygen, and Temperature......Page 38
1.3.4 Planning a Photochemical Synthesis......Page 40
1.4 Photochemical Steps in Synthetic Planning......Page 42
References......Page 45
2.1 Introduction......Page 48
2.1.1 Synthesis of Unstable Molecules......Page 50
2.2.1 Concerted Reactions......Page 53
2.2.2.1 Synthesis of Three-Membered Rings......Page 54
2.2.2.2 Synthesis of Cyclobutanes and Polycyclic Compounds......Page 56
2.2.3 Photoelimination of CO from Ketones in Solution......Page 58
2.2.4 Photoelimination of CO2 from Lactones......Page 62
2.2.5 Photoelimination of Sulfur from Sulfides, Sulfoxides, and Sulfones......Page 63
2.3 Reactions in the Solid State......Page 64
2.3.1 Reactivity and Stability in the Solid State......Page 65
2.3.2 Restricting the Fate of the Radical Intermediates in Solids......Page 66
2.3.3 Crystalline Diacyl Peroxides......Page 67
2.3.4.1 Early Observations......Page 73
2.3.4.2 Reactivity and Stability......Page 74
2.3.4.3 The RSE > 11 kcal mol -1 Condition......Page 76
2.3.4.4 Scope of the Reaction......Page 78
2.3.4.5 Reaction Enantiospecificity......Page 79
2.3.4.7 Quenching Effects......Page 80
2.3.4.8 Reaction Scale and Experimental Conditions......Page 82
References......Page 83
3.1 Introduction......Page 90
3.1.1 Scope and Mechanism......Page 91
3.2.1 H–C Addition (Hydroalkylation Reactions)......Page 92
3.2.1.1 Addition of Alkanes......Page 93
3.2.1.2 Addition of Alcohols (Hydrohydroxymethylation), Ethers, and (2-substituted) 1,3-Dioxolane(s)......Page 94
3.2.1.3 Addition of Amines (Hydroaminomethylation) or Amides......Page 95
3.2.1.4 Hydrofluoromethylation......Page 97
3.2.1.6 Hydroacylation and Hydrocarboxylation Reactions......Page 98
3.2.2 H–N Addition (Hydroamination)......Page 99
3.2.3 H–P Addition......Page 101
3.2.4 H–O Addition......Page 103
3.2.5 H–S Addition......Page 105
3.2.6 Addition of X-Y Reagents to Alkenes......Page 106
3.2.6.2 Addition with the Formation of C–C Bonds......Page 107
3.3 Addition to C–C Triple Bonds......Page 109
3.3.2 Addition of X–Y Reagents......Page 110
3.4 Concluding Remarks......Page 111
References......Page 112
4.1 Introduction......Page 118
4.2.1 Di-π-Methane Rearrangement of Barrelene, Benzobarrelene, Dibenzobarrelene, and Related Derivatives......Page 119
4.2.2 Di-π-Methane Rearrangement of Acyclic Systems......Page 123
4.2.3 Di-π-Methane Rearrangement in Natural Compounds......Page 126
4.3.1 Oxa-di-π-Methane Rearrangement of β,γ-Unsaturated Ketones and Aldehydes......Page 128
4.3.2 Aza-di-π-Methane Rearrangement......Page 132
4.3.3 Synthetic Applications of Oxa-di-π-Methane Rearrangement......Page 133
4.4.2 Novel Triplet Sensitizers for the Generation of Carbenes......Page 134
4.4.3 Metal-Catalyzed Cyclopropanation-Supported Photochemistry......Page 135
4.4.4 Novel Precursors of Carbenes......Page 136
4.5 Formation of a Cyclopropane via Intramolecular Hydrogen Abstraction......Page 137
4.5.1 Formation of Cyclopropanol via Intramolecular β-Hydrogen Abstraction......Page 138
4.5.2 Formation of Cyclopropane Ring via Intramolecular γ-Hydrogen Abstraction......Page 140
4.6.2 Intramolecular [3 + 2] Cycloaddition......Page 142
4.6.3 Application of the Photochemical [3 + 2] Cycloaddition in the Synthesis of Natural Products......Page 145
4.7.2 Aziridines......Page 146
References......Page 149
5.2 [2 + 2]-Photocycloaddition of Nonconjugated Alkenes......Page 160
5.3 [2 + 2]-Photocycloaddition of Aromatic Compounds......Page 167
5.4 Photochemical Electrocyclic Reactions......Page 173
5.5 Intramolecular γ-Hydrogen Abstraction (Yang Reaction)......Page 176
5.6 Metal-Catalyzed Reactions......Page 179
5.7 Other Methods......Page 180
References......Page 183
6.1 Introduction......Page 194
6.2.1 Cyclopentenones......Page 196
6.2.2 Cyclohexenones......Page 200
6.2.3 para-Quinones and Related Substrates......Page 204
6.3 [2 + 2]-Photocycloaddition of Vinylogous Amides and Esters (Substrate Classes A2 and A3)......Page 205
6.3.1.1 4-Hetero-2-Cyclopentenones......Page 206
6.3.1.2 4-Hetero-2-Cyclohexenones......Page 208
6.3.2 Exocyclic Heteroatom Q in β-Position (Substrate Class A3)......Page 209
6.4.1.1 α,β-Unsaturated Lactones......Page 212
6.4.1.2 α,β-Unsaturated Lactams......Page 215
6.4.1.3 Coumarins......Page 216
6.4.1.4 Quinolones......Page 217
6.4.1.5 Maleic Anhydride and Derivatives......Page 219
6.4.1.6 Sulfur Compounds......Page 220
6.4.2.1 1,3-Dioxin-4-ones......Page 221
6.4.2.2 4-Pyrimidinones......Page 223
6.4.3 Exocyclic Heteroatom Q in β-Position (Substrate Class A6)......Page 224
6.4.3.1 Lactones......Page 225
6.4.3.2 Lactams......Page 226
References......Page 228
7.1 Introduction......Page 240
7.2 The Generally Accepted Mechanism of the Paternò–Büchi Reaction......Page 243
7.3 Regioselective and Site-Selective Syntheses of Oxetanes......Page 244
7.4 Stereoselective Syntheses of Oxetanes......Page 249
References......Page 256
8.2 Formation of Five-Membered Rings: Intramolecular δ-H Abstraction......Page 264
8.2.1 Formation of Cyclopentanol Ring System......Page 265
8.2.1.1 Synthesis of Indanols......Page 266
8.2.2 Synthesis of Tetrahydrofuranols......Page 270
8.2.3 Synthesis of Pyrrolidine Derivatives......Page 273
8.3.1 Photofragmentation of Oxiranes to Carbonyl Ylides: Synthesis of Tetrahydrofurans......Page 277
8.3.2 Generation of Azomethine Ylides by the Photolysis of Aziridines: Synthesis of the Pyrrolidine Framework......Page 281
8.3.3 Vinyl Cyclopropane to Cyclopentene Rearrangement......Page 283
8.4 Photochemical Electrocyclization Reactions: Synthesis of Fused, Five-Membered Ring Compounds......Page 284
8.5.1 Radical Cation-Mediated Carbon–Carbon Bond Formation......Page 289
8.5.2 Radical Anion-Mediated Cyclizations......Page 295
8.5.3 Intramolecular Trapping of Radical Cations by Nucleophiles......Page 299
References......Page 302
9.2.1 Phthalimides as Electron Acceptors......Page 310
9.2.2 Aromatic Ketones as Electron Acceptors......Page 314
9.2.3 Chloroacetamides as Electron Acceptors......Page 315
9.2.4 Electron-Deficient Aromatic Compounds as Electron Acceptors......Page 316
9.3.1 Stilbene-Like Photocyclization......Page 318
9.3.3 Anilides and Enamides Photocyclization......Page 322
9.4 Photocycloaddition Reactions......Page 323
9.4.1 Photochemical Diels–Alder Reaction......Page 324
9.4.3 [4 + 4]-Photocycloaddition......Page 325
9.4.4 Transition Metal Template-Controlled Reactions......Page 327
9.5 Remote Intramolecular Hydrogen Abstraction......Page 330
9.6 Ring Contraction and Ring Enlargement......Page 331
9.7.3 Photocycloaddition of Aromatic Compounds......Page 334
References......Page 336
10.1 Introduction......Page 342
10.2.1 SRN1 Mechanism......Page 343
10.2.2 SN1 Mechanism......Page 345
10.3.1 Carbanions from Ketones, Esters, Acids, Amides, and Imides as the Nucleophiles......Page 346
10.3.2 Alkenes, Alkynes, Enols, and Vinyl Amines as the Nucleophiles......Page 349
10.3.3 Aryl Alkoxide and Aryl Amide Anions as the Nucleophiles......Page 352
10.3.4 Cyanide Ions as the Nucleophile......Page 354
10.4.1 Tin Nucleophiles......Page 355
10.4.2 Sulfur Nucleophiles......Page 356
10.5.1 Consecutive SRN1–Pd(0)-Catalyzed Crosscoupling Reactions......Page 357
10.5.2 Photo-SN1 as an Alternative to Metal Catalysis......Page 359
10.6.1 Carbocycles......Page 361
10.6.2 Nitrogen Heterocycles......Page 364
10.6.3 Oxygen Heterocycles......Page 367
References......Page 369
11.1 Introduction......Page 376
11.2.1 Background Information......Page 377
11.2.2 Adamantyl-Substituted Alkenes......Page 378
11.2.3 Alkoxy-Substituted Alkenes......Page 379
11.2.4.2 Electron-Transfer Photooxidation......Page 380
11.3.1 Background Information......Page 381
11.3.2.1 Benzenes......Page 382
11.3.2.2 Naphthalenes......Page 384
11.3.2.3 Anthracenes, Polyacenes, and Carbon Nanotubes......Page 385
11.3.4.2 Cyclopentadienes and Cyclohexadienes......Page 387
11.3.4.3 Heterocycles and Cyclohexatriene......Page 388
11.4.2 Simple Alkenes......Page 391
11.4.4 Summary......Page 393
11.5.2.1 Phenyl-Substituted Alkenes......Page 394
11.5.2.2 Cyclic Alkenes......Page 395
11.5.4 Rearrangements to Spiro Compounds......Page 397
11.5.5 Summary......Page 399
References......Page 400
12.1 Introduction......Page 410
12.2.1 Pyrroles......Page 411
12.2.2 Furans......Page 414
12.2.3 Thiophenes......Page 415
12.3.1 Pyrazoles......Page 416
12.3.2 Imidazoles......Page 417
12.3.3 Oxazoles......Page 421
12.3.4 Thiazoles......Page 423
12.4.1 Oxadiazoles......Page 425
12.4.2 Triazoles......Page 427
12.4.3 Thiadiazoles......Page 428
12.6.1 Azepines......Page 429
12.6.2 Diazepines......Page 430
12.6.3 Oxazepines......Page 432
12.7 Concluding Remarks......Page 433
References......Page 434
13.1 Introduction......Page 440
13.2.1 Ortho-Nitrobenzyl Alcohol Derivatives......Page 441
13.2.2 Benzyl Alcohol Derivatives......Page 444
13.2.3.1 Norrish Type II......Page 446
13.2.3.4 Silicon Ethers......Page 447
13.2.4.1 Cinnamyl Esters......Page 448
13.2.5.1 Mechanism......Page 449
13.2.6.1 Mechanism......Page 451
13.2.7 Indolines......Page 452
13.3 Chromatic Orthogonality......Page 453
13.4 Two-Photons Absorption......Page 454
13.5 Concluding Remarks......Page 455
13.6 Appendix......Page 456
References......Page 462
Index......Page 472