Foreword ....................................................... xv
Preface ...................................................... xvii
Contributors .................................................. xix
1 Silver Alkyls, Alkenyls, Aryls, and Alkynyls in Organic
Synthesis .................................................... 1
Rebecca H. Pouwer and Craig M. Williams
1.1 Introduction ............................................ 2
1.2 Csp3-Ag ................................................. 2
1.2.1 Synthesis, Stability, and Reactivity of
Alkylsilver Compounds ............................ 2
1.2.2 Synthesis and Stability of Perfluoroalkylsilver
Compounds ........................................ 7
1.2.3 Reactivity of Perfluoroalkylsilver Compounds ..... 9
1.3 Csp2-Ag ................................................ 10
1.3.1 Synthesis and Stability of Arylsilver
Compounds ....................................... 10
1.3.2 Reactivity of Arylsilver Compounds .............. 11
1.3.3 Synthesis and Stability of Perfluoroarylsilver
Compounds ....................................... 12
1.3.4 Reactivity of Perfluoroarylsilver Compounds ..... 13
1.3.5 Synthesis, Stability, and Reactivity of
Alkenylsilver Compounds ......................... 13
1.3.6 Synthesis and Reactivity of Allenylsilver
Compounds ....................................... 15
1.3.7 Synthesis of Perfluoroalkenylsilver Compounds ... 16
1.3.8 Reactivity of Perfluoroalkenylsilver
Compounds ....................................... 17
1.3.9 Synthesis and Reactivity of Silver-Substituted
Diazomethyl Compounds ........................... 17
1.4 Csp-Ag ................................................. 18
1.4.1 Synthesis of Silver Acetylides .................. 19
1.4.2 Reactivity of Silver Acetylides ................. 20
1.4.2.1 Addition to Activated Carbonyls and
Iminium Ions ........................... 20
1.4.2.2 Nucleophilic Substitution of
Activated Heteroaromatics .............. 24
1.4.2.3 Reaction with Alkyl Halides ............ 25
1.4.2.4 Coupling Reactions ..................... 27
1.4.2.5 Reactions with Non-carbon
Electrophiles .......................... 30
1.4.2.6 Fragmentation .......................... 32
1.4.2.7 Desilylation ........................... 32
1.5 Conclusion ............................................. 36
References .................................................. 37
2 Cycloaddition Reactions ..................................... 43
Alex M. Szpilman and Erick M. Carreira
2.1 Introduction ........................................... 44
2.2 [2+2] Cycloadditions ................................... 44
2.3 [3+2] Cycloadditions ................................... 46
2.3.1 [3+2] Cycloadditions of Azomethine Ylides ....... 47
2.3.1.1 Discovery and Development of the
Silver-Catalyzed [3+2] Cycloaddition
of Azomethine Ylides ................... 47
2.3.1.2 Auxiliary-Based Asymmetric [3+2]
Cycloadditions ......................... 50
2.3.1.3 Catalytic Asymmetric [3+2]
Cycloadditions ......................... 58
2.3.1.4 Selected Applications and Extensions
of Azomethine [3+2] Cycloadditions ..... 66
2.3.2 Other [3+2] Cycloadditions ...................... 71
2.4 [3+3] Cycloadditions ................................... 73
2.5 [4+2] Cycloadditions ................................... 74
2.6 Concluding Remarks ..................................... 78
References .................................................. 79
3 Sigmatropic Rearrangements and Related Processes Promoted
by Silver ................................................... 83
Jean-Marc Weibel, Auréelien Blanc, and Patrick Pale
3.1 Introduction ........................................... 84
3.2 Wolff and Arndt-Eistert Rearrangements and Related
Reactions .............................................. 84
3.3 Ring Rearrangements .................................... 86
3.3.1 Halogenoamines .................................. 86
3.3.2 Cyclopropane Derivatives ........................ 88
3.3.3 Cubane Derivatives .............................. 92
3.3.4 Halogenocyclopropane Derivatives ................ 93
3.4 [3,3]-Sigmatropic Rearrangements ....................... 95
3.4.1 With Асуl as Migrating Groups ................... 95
3.4.2 With Vinyl as Migrating Groups .................. 98
3.4.3 With Migrating Groups Analogous to Acyl ........ 101
3.4.4 [3,3]-Sigmatropic Rearrangement and
Cyclization Cascades ........................... 102
3.5 [2,3]-Sigmatropic Rearrangements ...................... 107
3.6 [l,2]-Sigmatropic Rearrangements ...................... 108
3.6.1 1,2-Aryl or Alkenyl Migration .................. 108
3.6.2 1,2-Alkyl Migration ............................ 110
3.6.3 1,2- or 1,5-Alkyl Migration .................... 110
3.6.4 1,2 versus 3,3 Migrations ...................... 111
3.7 Miscellaneous ......................................... 113
3.8 Conclusion ............................................ 113
References ................................................. 114
4 Silver(I)-Mediated Electrocyclic Processes ................. 117
Tina N. Grant and Frederick G. West
4.1 Introduction .......................................... 117
4.1.1 Ring-Opening Reactions of Halocyclopropanes .... 118
4.1.2 Silver(I)-Assisted Ring-Opening Reactions ...... 120
4.2 Nucleophilic Trapping of Cationic Intermediates ....... 121
4.2.1 Solvolysis Reactions ........................... 121
4.2.2 Intramolecular Trapping with
Heteronucleophiles ............................. 124
4.2.3 Diastereoselective Reactions ................... 127
4.2.4 Carbon-Carbon Bond Formation ................... 129
4.3 The Silver(I)-Promoted Nazarov Reaction ............... 132
4.3.1 Development and Initial Findings ............... 133
4.3.2 Interrupted Nazarov Reactions .................. 135
4.4 Concluding Remarks .................................... 139
References ................................................. 139
5 Silver-Catalyzed Cycloisomerization Reactions .............. 143
Philippe Belmont
5.1 Introduction .......................................... 143
5.2 Cycloisomerization of C=0 onto C=C=C .................. 144
5.3 Cycloisomerization of C=0 onto C≡C .................... 148
5.4 Cycloisomerization of C=N onto C=C=C .................. 152
5.5 Cycloisomerization of C=N onto C≡C .................... 153
5.6 Ene-Yne Cycloisomerization: C=C onto C≡C .............. 157
5.7 Other Transformations ................................. 160
5.8 Conclusion ............................................ 162
References ................................................. 162
6 Silver-Catalyzed Nitrene Transfer Reactions ................ 167
Zigang Li, David A. Capretto, and Chuan He
6.1 Introduction .......................................... 167
6.2 Aziridination ......................................... 169
6.2.1 Chloramine-T as Nitrene Precursor .............. 169
6.2.2 Iminoiodanes as Nitrene Precursors ............. 169
6.2.3 Heterogenous Silver Catalysis .................. 172
6.3 Sulfide and Sulfoxide Imination ....................... 172
6.4 Amidation ............................................. 173
6.4.1 Intramolecular Amidation ....................... 173
6.4.2 Intermolecular Amination with Phenanthroline
Ligands ........................................ 174
6.4.3 Intermolecular Amination Based on
Pyrazolylborate Ligands ........................ 177
6.5 Conclusion ............................................ 180
References ................................................. 180
7 Silver-Catalyzed Silylene Transfer ......................... 183
Tom G. Driver
7.1 Introduction .......................................... 183
7.2 Reactivity and Attributes of Metal Silylenoids and
Silylmetal Complexes .................................. 184
7.2.1 Synthesis of Transition Metal Complexes of
Silylenes ...................................... 184
7.2.2 Reactivity of Transition Metal Silylenoids ..... 187
7.2.3 Transition Metal Silylenoid Complex-Catalyzed
Нуdrosilation Reactions ........................ 187
7.2.4 Transition Metal Silylenoid-Catalyzed Atom
Transfer Reactions ............................. 189
7.3 Silacyclopropanes as Important Synthetic
Intermediates ......................................... 190
7.4 Silver-Mediated Transfer of Di-tert-Butylsilylene to
Olefins ............................................... 192
7.5 Silver-Mediated Transfer of Di-tert-Butylsilylene to
Acetylenes ............................................ 200
7.6 Silver-Mediated Transfer of Di-tert-Butylsilylene to
Carbonyl Compounds .................................... 207
7.7 Silver-Mediated Transfer of Di-tert-Butylsilylene to
Imines ................................................ 214
7.8 Silver-Mediated Di-tert-Butylsilylene Insertion into
C-O Bonds ............................................. 219
7.9 Conclusion ............................................ 221
References ................................................. 222
8 Silver Carbenoids .......................................... 229
Carl J. Lovely
8.1 Introduction .......................................... 229
8.2 Wolff Rearrangement ................................... 230
8.3 Carbene Transfer Reactions to π Bonds ................. 232
8.3.1 Aziridination .................................. 232
8.3.2 Cyclopropanation ............................... 233
8.4 Formation and Reactions of Ylides ..................... 234
8.4.1 С-Hal Addition-Rearrangement ................... 234
8.4.2 C-S Addition-Rearrangement ..................... 241
8.5 C-H Insertion ......................................... 242
8.6 N-H Insertion ......................................... 243
8.7 Ring Expansion Reactions .............................. 250
8.8 Intermediacy of Silver Carbenes ....................... 250
8.9 Miscellaneous Reactions Involving Silver Carbenoids ... 253
8.10 Summary ............................................... 254
Acknowledgments ............................................ 255
References ................................................. 255
9 Aldol and Related Processes ................................ 259
Masanori Kawasaki and Hisashi Yamamoto
9.1 Introduction .......................................... 259
9.2 Allylation Reaction Using Allyltributyltin ............ 260
9.3 Allylation Reaction Using Allylsilanes ................ 264
9.4 Aldol Reaction Using Tin Enolates ..................... 268
9.5 Aldol Reaction Using Silyl Enol Ethers ................ 271
9.6 Mannich Reaction ...................................... 276
9.7 Nitrosoaldol Reaction ................................. 277
9.8 Aldol Reaction with Azodicarboxylate .................. 281
9.9 Conclusion ............................................ 281
References ................................................. 282
10 Coupling Reactions Promoted by Silver ...................... 285
Jean-Marc Weibel, Aurelien Blanc, and Patrick Pale
10.1 Introduction .......................................... 286
10.2 sp3-sp3 Coupling Reactions Promoted by Silver Salts ... 286
10.3 sp3-sp2 Coupling Reactions Promoted by Silver Salts ... 289
10.4 sp3-sp Coupling Reactions Promoted by Silver Salts .... 290
10.5 sp2-sp2 Coupling Reactions Promoted by Silver Salts ... 291
10.5.1 Homocoupling of Vinyl- or Arylsilver Species ... 292
10.5.2 Organosilver Species as Nucleophilic
Reagents ....................................... 293
10.5.3 Silver as a Lewis Acid Reagent ................. 294
10.5.4 Silver as a Halogen Scavenger .................. 297
10.5.4.1 Silver in Pd-Catalyzed Couplings ...... 298
10.5.4.2 Silver in PdII-Promoted Electrophilic
Substitution of Arenes (C-H
Activation) ........................... 306
10.5.4.3 Silver as Reagent for
Decarboxylative Coupling .............. 309
10.6 sp2-sp Coupling Reactions Promoted by Silver Salts .... 310
10.6.1 Organosilver Species as Nucleophilic
Reagents ....................................... 311
10.6.2 Organosilver Species in Transmetallations ...... 314
10.6.3 Silver as a Lewis Acid Reagent ................. 315
10.6.4 Organosilver Species as Intermediates in
Catalyzed Enyne or Arylyne Synthesis ........... 316
10.7 sp-sp Coupling Reactions Promoted by Silver Salts ..... 322
10.8 Conclusion ............................................ 323
References ................................................. 324
11 Supramolecular Chemistry of Silver ......................... 329
Wei-Yin Sun, Zheng-Shuai Bai, and Jin-Quan Yu
11.1 Introduction .......................................... 329
11.2 Cage-Like Complexes ................................... 330
11.3 Tube-Like Compounds ................................... 337
11.4 Polycatenanes with Silver(I) .......................... 339
11.5 Polyrotaxanes with Silver(I) .......................... 342
11.6 Silver(I) Coordination Polymers with Specific
Topology .............................................. 345
11.7 Conclusion ............................................ 350
Acknowledgments ............................................ 352
References ................................................. 352
12 A Critical Comparison: Copper, Silver, and Gold ............ 357
A. Stephen K. Hashmi
12.1 Introduction .......................................... 358
12.2 Reactions Catalyzed by Copper, Silver, or Gold ........ 358
12.2.1 Aldehyde-Alkyne-Amine Coupling ................. 358
12.2.2 Carbene Insertion Reactions .................... 360
12.2.3 In Silico Comparison of Organocopper(I),
Organosilver(I), and Organogold(I)-Ate
Compounds ...................................... 361
12.2.4 Cyclization of ortho-alkynylbenzaldehydes ...... 362
12.2.5 Allenyl Ketones: The Cycloisomerization to
Furans ......................................... 362
12.2.6 A Thiol in the Substrate: The Cyclization of
α-Thioallenes .................................. 364
12.2.7 Furans by Propargyl Claisen Reaction ........... 365
12.2.8 Tandem Cyclization/Pinacol Rearrangement ....... 366
12.2.9 Furanones by Domino Heterocyclization/1,2
Shift .......................................... 366
12.2.10 Conia-ene Reaction ............................ 368
12.3 Reactions Catalyzed by Silver or Gold ................. 368
12.3.1 Cyclization of N-Propargylcarboxamides ......... 368
12.3.2 Dake's Pyrrole Synthesis ....................... 369
12.3.3 Combination with Organocatalysis ............... 369
12.3.4 Vinylallenes Deliver Cyclopentadienes .......... 370
12.3.5 α-Pyrones by a Cascade Reaction ................ 371
12.3.6 Dihydrofurans from Propargyl Esters ............ 371
12.3.7 Methylene Butyrolactones by Addition of
Carboxylates to Alkynes ........................ 372
12.3.8 Hydroarylation of Allenes ...................... 373
12.3.9 Different Products by Silver and Gold
Catalysts ...................................... 373
12.3.9.1 The Epoxide-Alkyne Reaction ........... 373
12.3.9.2 The Carbonyl-Alkyne Reaction .......... 374
12.4 Reactions Catalyzed by Copper or Silver ............... 374
12.4.1 General Trends ................................. 374
12.4.2 Pyrroles by Hydroamination ..................... 374
12.4.3 Copper/Silver Cocatalysis ...................... 375
12.4.4 Carbonylations ................................. 375
12.5 Conclusion ............................................ 376
References ................................................. 376
Index ......................................................... 381
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