Contributors ................................................. xiii
Chapter 1 From Gold in Nature to Gold Catalysts ................ 1
Søren Kramer and Fahim Gagosz
1.1 The Gold Element: An Overview .............................. 1
1.1.1 History of gold ..................................... 1
1.1.2 Abundance, production, and stocks ................... 2
1.1.3 Demand and supply ................................... 3
1.1.4 Price ............................................... 3
1.1.5 General physical and chemical properties ............ 4
1.1.6 Applications ........................................ 4
1.2 History of Homogeneous Gold Catalysis ...................... 5
1.3 General Reactivity of Electrophilic Gold Species ........... 9
1.4 Gold Catalysts ............................................ 14
1.4.1 Inorganic gold catalysts ........................... 16
1.4.2 Gold complexes ..................................... 19
1.4.3 Chiral catalysts ................................... 34
1.5 Conclusion ................................................ 38
References ................................................ 40
Chapter 2 Homogeneous Gold-Catalyzed Oxidation and
Reduction Reactions ............................................ 51
Liming Zhang
2.1 Introduction .............................................. 51
2.2 Homogeneous Gold-Catalyzed Oxidation Reactions
with External Oxidants .................................... 52
2.2.1 Alkyne or allene as substrate ...................... 52
2.2.2 Alkenes as substrates .............................. 67
2.2.3 Alcohol and sulfides as substrates ................. 71
2.3 Homogeneous Gold-Catalyzed Intramolecular
Redox Reactions ........................................... 71
2.3.1 With tether oxidants ............................... 71
2.3.2 Involving hydride migration ........................ 77
2.4 Homogeneous Gold-Catalyzed Reductions ..................... 79
2.5 Summary ................................................... 80
2.6 Acknowledgment ............................................ 80
References ................................................ 81
Chapter 3 Gold-Catalyzed Addition of Carbon Nucleophiles to
C-C Multiple Bonds, Carbonyls, and other Electrophiles ......... 87
Bryon L. Simmons and Hong C. Shen
3.1 Introduction .............................................. 87
3.2 Addition of Carbon Nucleophiles to Alkynes ................ 88
3.2.1 Addition of enols, silyl enol ethers, and silyl
ketene amides to alkynes ........................... 88
3.2.2 Addition of enamine derivatives to alkynes ......... 92
3.2.3 Addition of arenes to alkynes ...................... 93
3.2.4 Addition of alkenes to alkynes ..................... 99
3.2.5 Addition of allyls to C-C multiple bonds .......... 104
3.2.6 Addition of allenes to alkynes .................... 107
3.2.7 Addition of carbenes to alkynes ................... 108
3.3 Addition of Carbon Nucleophiles to Allenes ............... 108
3.4 Addition of Carbon Nucleophiles to Alkenes ............... 114
3.5 Addition of Carbon Nucleophiles to Carbonyls ............. 119
3.6 Addition of Carbon Nucleophiles to Iminiums .............. 122
3.7 Addition of Arenes and Alkenes to Miscellaneous
Electrophiles ............................................ 122
3.8 Conclusion ............................................... 129
References ............................................... 130
Chapter 4 Gold-Catalyzed Addition of Heteroatom Nucleophile
to C-C Multiple Bond .......................................... 137
Naoki Asao, Naoya Hatakeyama and Yoshinori Yamamoto
4.1 Introduction ............................................. 137
4.2 Nitrogen Nucleophiles .................................... 137
4.2.1 Addition to alkynes ............................... 137
4.2.2 Addition to allenes ............................... 141
4.2.3 Addition to alkenes and dienes .................... 143
4.3 Oxygen Nucleophiles ...................................... 145
4.3.1 Addition to alkynes ............................... 145
4.3.2 Addition to allenes ............................... 161
4.3.3 Addition to alkenes and dienes .................... 162
4.4 Sulfur Nucleophiles ...................................... 164
4.5 Other Heteroatom Nucleophiles ............................ 165
4.6 Conclusion ............................................... 166
References ............................................... 166
Chapter 5 Gold-Catalyzed Synthesis of Heterocycles ........... 175
Antonio Arcadi
5.1 Introduction ............................................. 175
5.2 Synthesis of Heterocycles via Gold-Catalyzed Heteroatom
Addition to Unsaturated C-C Bonds ........................ 176
5.2.1 Synthesis of heterocyclic compounds through
intermolecular hydrofunctionalization of alkynes .. 177
5.2.2 Synthesis of heterocyclic compounds through
intramolecular hydrofunctionalization of
alkynes, allenes, and alkenes ..................... 180
5.2.3 Heterocyclization of alkynes tethered with
carbonyl groups ................................... 188
5.2.4 Gold-catalyzed migratory cyclizations ............. 191
5.3 Synthesis of Heterocyclic Derivatives through
Gold-Catalyzed Cyclization of Polyunsaturated Compounds .. 193
5.4 Synthesis of Heterocyclic Compounds via oc-Oxo Gold
Carbenoid ................................................ 196
5.5 Synthesis of Heterocyclic Derivatives through Gold-
Catalyzed Cycloaddition Reactions ........................ 201
5.6 Synthesis of Heterocyclic Derivatives through Gold-
Catalyzed Activation of Carbonyl Groups and Alcohols ..... 203
5.7 Synthesis of Heterocyclic Compounds through Gold-
Mediated C-H Bond Functionalization ...................... 206
5.7.1 Direct C-H functionalization of heterocycles ...... 206
5.7.2 Intramolecular gold-catalyzed hydroarylation
reactions ......................................... 208
5.7.3 Alkyne C-H and С 3-H functionalization ............ 211
5.8 Gold-Catalyzed Domino Cyclization/Oxidative Coupling
Reactions ................................................ 212
5.9 Conclusions .............................................. 215
References ............................................... 217
Chapter 6 Gold-Catalyzed Multi-Component Reactions ........... 225
Rachid Skouta and Chao-Jun Li
6.1 Introduction ............................................. 225
6.2 Gold-Catalyzed Three-Component Reactions ................. 226
6.2.1 Aldehydes, terminal alkynes, and amines ........... 226
6.2.2 Aldehydes, terminal alkynes, and
triethylorthoformate .............................. 234
6.2.3 Aldehydes, ketones, and carbamates ................ 234
6.2.4 Imines, acyl chlorides, and terminal alkynes ...... 236
6.2.5 Acetylenedicarboxylates, quinoline/isoquinoline,
and terminal alkynes .............................. 237
6.2.6 (Arylmethylene)cyclopropylcarbinols, terminal
alkynes, and alcohols ............................. 239
6.2.7 Amines, internal alkynes, and terminal alkynes .... 240
6.2.8 Alkenes, boronic acid, and oxygen nucleophiles .... 242
6.3 Gold-Catalyzed Three-Component Reactions/Tandem
Cyclization .............................................. 243
6.3.1 Aldehydes, terminal alkynes, and amines/
Cycloisomerization ................................ 243
6.3.2 Glyoxylic acid, alkynes, and amines/
Intramolecular cyclization ........................ 244
6.3.3 Enantioselective [4 + 2] cycloaddition/
Intramolecular hydroamination ..................... 246
6.4 Concluding Remarks ....................................... 247
6.5 Acknowledgments .......................................... 247
References ............................................... 248
Chapter 7 Gold Catalysis on Tandem and Cascade Reactions ..... 253
Rai-Shung Liu
7.1 Introduction ............................................. 253
7.2 Oxo Alkynes .............................................. 254
7.3 Oxodienes ................................................ 263
7.4 Iminoalkynes ............................................. 266
7.5 Aminoalkynes ............................................. 266
7.6 Nitroalkyne .............................................. 266
7.7 Alkynyl Nitrone .......................................... 267
7.8 Allenyl Acetals .......................................... 268
7.9 Epoxyalkynes ............................................. 269
7.10 Alkynyl Hydroxylamine .................................... 270
7.11 Conclusion ............................................... 271
References ............................................... 271
Chapter 8 Cycloisomerization Reactions of 1, N-Enynes ........ 275
Nuria Huguet and Antonio M. Echavarren
8.1 Introduction ............................................. 275
8.2 Gold Complexes ........................................... 275
8.3 Gold-Catalyzed Cyclization of 1, n-Enynes ................ 278
8.3.1 Gold-catalyzed cycloisomerizations of
1,6-enynes ........................................ 278
8.3.2 Gold-catalyzed cycloisomerizations and skeletal
rearrangement of 1, 5-enynes ...................... 293
8.3.3 Gold-catalyzed cycloisomerizations and skeletal
rearrangement of 1, n-enynes (n > 6) .............. 309
8.3.4 Intermolecular reactions of alkynes with alkenes
and [2 + 2] cycloadditions ........................ 311
References ............................................... 314
Chapter 9 Gold-Catalyzed Reactions of Propargylic Esters ..... 331
Louis Fensterbank, Jean-Philippe Goddard, Max Malacria and
Antoine Simonneau
9.1 Introduction ............................................. 331
9.2 1,2-O-Acyl Migrations .................................... 335
9.2.1 Scope and applications ............................ 335
9.2.2 Intermolecular processes .......................... 343
9.3 1,3-O-Acyl Migrations .................................... 345
9.3.1 Intramolecular nucleophilic additions onto the
gold-activated allenyl ester ...................... 346
9.3.2 Allenyl esters as nucleophiles in allenyne
systems ........................................... 355
9.3.3 Cycloadditions and electrocyclizations ............ 362
9.3.4 Access to unsaturated carbonyl derivatives from
propargylic esters ................................ 372
9.3.5 Access to (1,3)-dienes from propargylic esters .... 376
9.4 Conclusion ............................................... 380
References ............................................... 381
Chapter 10 Gold-Catalyzed Cross-Coupling Reactions ........... 393
Suzanne A. Blum
10.1 Introduction ............................................. 393
10.2 Dual-Catalytic Gold and Palladium Cross-Coupling
Reactions ................................................ 394
10.2.1 Mechanistic reaction design considerations ........ 394
10.2.2 Simultaneous activation: Gold-catalyzed
cyclization initiates oxidative addition of
palladium ......................................... 395
10.2.3 Tandem reactivity: Sonogashira-type cross-
couplings with gold and palladium ................. 399
10.3 Fundamental Understanding through Stoichiometric
Experiments .............................................. 401
10.3.1 Palladium-catalyzed cross-coupling
of stoichiometric organogold reagents ............. 402
10.3.2 Mechanism: Single-step transmetalation ............ 405
10.3.3 Other metals ...................................... 406
10.4 Challenges ............................................... 408
10.4.1 Gold redox reactivity ............................. 408
10.4.2 Dual-catalytic turnover strategies ................ 409
10.5 Outlook .................................................. 409
References ............................................... 410
Chapter 11 Gold-Catalyzed Reactions: A Computational
Approach ...................................................... 413
Elena Soriano and Jose Marco-Contelles
11.1 Introduction ............................................. 413
11.2 Theoretical Considerations ............................... 415
11.2.1 Relativistic effects .............................. 415
11.2.2 Structure and bonding properties of the
reactant complexes ................................ 418
11.3 Mechanistic Considerations ............................... 428
11.3.1 Alkyne activation and reactivity .................. 428
11.3.2 Key intermediates: Carbene or carbocation ......... 430
11.3.3 Other mechanistic considerations .................. 436
11.4 Acknowledgment ........................................... 438
References ............................................... 438
Chapter 12 Recent Developments in Asymmetric Catalysis ....... 445
Patrick Y. Toullec, Alexandre Pradal and Véronique Michelet
12.1 Reactivity of Carbonyl- and Imine-Functionalized
Derivatives .............................................. 448
12.2 Reactivity of Functionalized Alkenes ..................... 454
12.2.1 Hydrogenation and protonation reactions ........... 454
12.2.2 Nucleophilic additions to alkenes or alkenyl
intermediates ..................................... 455
12.3 Gold-Catalyzed Activation of Allenes ..................... 460
12.3.1 Enantioselective addition of oxygen nucleophiles
to allenes ........................................ 460
12.3.2 Enantioselective addition of nitrogen
nucleophiles to allenes ........................... 463
12.3.3 Enantioselective addition of carbon nucleophiles
to allenes ........................................ 467
12.4 Gold-Catalyzed Activation of Alkynes ..................... 472
12.4.1 Rearrangement of propargylic esters and
reactivity of carbenoid intermediates ............. 472
12.4.2 Addition of carbon or heteroatom to alkynes ....... 477
12.4.3 Cycloisomerization reactions of enynes ............ 482
12.5 Conclusion ............................................... 492
References ............................................... 493
Chapter 13 Gold Catalysis in Natural Product Synthesis ........ 501
Michael R. Gesinski and F. Dean Toste
13.1 Introduction ............................................. 501
13.2 Addition of Heteroatoms .................................. 502
13.2.1 Hydration of alkynes: Synthesis of ketones ........ 502
13.2.2 Intramolecular hydroalkoxylations ................. 504
13.2.3 Spiroketalization ................................. 508
13.2.4 Cyclization via pyrylium intermediates ............ 511
13.2.5 1,2- and 1,3-Acyl migration ....................... 512
13.2.6 Hydrocarboxylation ................................ 516
13.2.7 Hydroamination .................................... 518
13.2.8 Rearrangements of N-Oxides ........................ 521
13.3 Enyne Cyclizations ....................................... 523
13.3.1 The Conia-ene reaction ............................ 523
13.3.2 Enyne-pinacol cascade reactions ................... 525
13.3.3 Formal [2 + 2 + 2] enyne/carbonyl cycloadditions .. 526
13.3.4 Other cascade reactions ........................... 526
13.4 Hydroarylation Reactions ................................. 528
13.5 Aldol Reactions .......................................... 530
13.6 Conclusion ............................................... 531
References ............................................... 532
Index ......................................................... 537
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