Contributors |
|
xiii | |
|
Chapter 1 From Gold in Nature to Gold Catalysts |
|
|
1 | (50) |
|
|
|
1.1 The Gold Element: An Overview |
|
|
1 | (4) |
|
|
1 | (1) |
|
1.1.2 Abundance, production, and stocks |
|
|
2 | (1) |
|
|
3 | (1) |
|
|
3 | (1) |
|
1.1.5 General physical and chemical properties |
|
|
4 | (1) |
|
|
4 | (1) |
|
1.2 History of Homogeneous Gold Catalysis |
|
|
5 | (4) |
|
1.3 General Reactivity of Electrophilic Gold Species |
|
|
9 | (5) |
|
|
14 | (24) |
|
1.4.1 Inorganic gold catalysts |
|
|
16 | (3) |
|
|
19 | (15) |
|
|
34 | (4) |
|
|
38 | (13) |
|
|
40 | (11) |
|
Chapter 2 Homogeneous Gold-Catalyzed Oxidation and Reduction Reactions |
|
|
51 | (36) |
|
|
|
51 | (1) |
|
2.2 Homogeneous Gold-Catalyzed Oxidation Reactions with External Oxidants |
|
|
52 | (19) |
|
2.2.1 Alkyne or allene as substrate |
|
|
52 | (15) |
|
2.2.2 Alkenes as substrates |
|
|
67 | (4) |
|
2.2.3 Alcohol and sulfides as substrates |
|
|
71 | (1) |
|
2.3 Homogeneous Gold-Catalyzed Intramolecular Redox Reactions |
|
|
71 | (8) |
|
2.3.1 With tether oxidants |
|
|
71 | (6) |
|
2.3.2 Involving hydride migration |
|
|
77 | (2) |
|
2.4 Homogeneous Gold-Catalyzed Reductions |
|
|
79 | (1) |
|
|
80 | (1) |
|
|
80 | (7) |
|
|
81 | (6) |
|
Chapter 3 Gold-Catalyzed Addition of Carbon Nucleophiles to C-C Multiple Bonds, Carbonyls, and other Electrophiles |
|
|
87 | (50) |
|
|
|
|
87 | (1) |
|
3.2 Addition of Carbon Nucleophiles to Alkynes |
|
|
88 | (20) |
|
3.2.1 Addition of enols, silyl enol ethers, and silyl ketene amides to alkynes |
|
|
88 | (4) |
|
3.2.2 Addition of enamine derivatives to alkynes |
|
|
92 | (1) |
|
3.2.3 Addition of arenes to alkynes |
|
|
93 | (6) |
|
3.2.4 Addition of alkenes to alkynes |
|
|
99 | (5) |
|
3.2.5 Addition of allyls to C--C multiple bonds |
|
|
104 | (3) |
|
3.2.6 Addition of allenes to alkynes |
|
|
107 | (1) |
|
3.2.7 Addition of carbenes to alkynes |
|
|
108 | (1) |
|
3.3 Addition of Carbon Nucleophiles to Allenes |
|
|
108 | (6) |
|
3.4 Addition of Carbon Nucleophiles to Alkenes |
|
|
114 | (5) |
|
3.5 Addition of Carbon Nucleophiles to Carbonyls |
|
|
119 | (3) |
|
3.6 Addition of Carbon Nucleophiles to Iminiums |
|
|
122 | (1) |
|
3.7 Addition of Arenes and Alkenes to Miscellaneous Electrophiles |
|
|
122 | (7) |
|
|
129 | (8) |
|
|
130 | (7) |
|
Chapter 4 Gold-Catalyzed Addition of Heteroatom Nucleophile to C--C Multiple Bond |
|
|
137 | (38) |
|
|
|
|
|
137 | (1) |
|
4.2 Nitrogen Nucleophiles |
|
|
137 | (8) |
|
4.2.1 Addition to alkynes |
|
|
137 | (4) |
|
4.2.2 Addition to allenes |
|
|
141 | (2) |
|
4.2.3 Addition to alkenes and dienes |
|
|
143 | (2) |
|
|
145 | (19) |
|
4.3.1 Addition to alkynes |
|
|
145 | (16) |
|
4.3.2 Addition to allenes |
|
|
161 | (1) |
|
4.3.3 Addition to alkenes and dienes |
|
|
162 | (2) |
|
|
164 | (1) |
|
4.5 Other Heteroatom Nucleophiles |
|
|
165 | (1) |
|
|
166 | (9) |
|
|
166 | (9) |
|
Chapter 5 Gold-Catalyzed Synthesis of Heterocycles |
|
|
175 | (50) |
|
|
|
175 | (1) |
|
5.2 Synthesis of Heterocycles via Gold-Catalyzed Heteroatom Addition to Unsaturated C--C Bonds |
|
|
176 | (17) |
|
5.2.1 Synthesis of heterocyclic compounds through intermolecular hydrofunctionalization of alkynes |
|
|
177 | (3) |
|
5.2.2 Synthesis of heterocyclic compounds through intramolecular hydrofunctionalization of alkynes, allenes, and alkenes |
|
|
180 | (8) |
|
5.2.3 Heterocyclization of alkynes tethered with carbonyl groups |
|
|
188 | (3) |
|
5.2.4 Gold-catalyzed migratory cyclizations |
|
|
191 | (2) |
|
5.3 Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Cyclization of Polyunsaturated Compounds |
|
|
193 | (3) |
|
5.4 Synthesis of Heterocyclic Compounds via α-Oxo Gold Carbenoid |
|
|
196 | (5) |
|
5.5 Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Cycloaddition Reactions |
|
|
201 | (2) |
|
5.6 Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Activation of Carbonyl Groups and Alcohols |
|
|
203 | (3) |
|
5.7 Synthesis of Heterocyclic Compounds through Gold-Mediated C-H Bond Functionalization |
|
|
206 | (6) |
|
5.7.1 Direct C-H functionalization of heterocycles |
|
|
206 | (2) |
|
5.7.2 Intramolecular gold-catalyzed hydroarylation reactions |
|
|
208 | (3) |
|
5.7.3 Alkyne C--H and Csp3--H functionalization |
|
|
211 | (1) |
|
5.8 Gold-Catalyzed Domino Cyclization/Oxidative Coupling Reactions |
|
|
212 | (3) |
|
|
215 | (10) |
|
|
217 | (8) |
|
Chapter 6 Gold-Catalyzed Multi-Component Reactions |
|
|
225 | (28) |
|
|
|
|
225 | (1) |
|
6.2 Gold-Catalyzed Three-Component Reactions |
|
|
226 | (17) |
|
6.2.1 Aldehydes, terminal alkynes, and amines |
|
|
226 | (8) |
|
6.2.2 Aldehydes, terminal alkynes, and triethylorthoformate |
|
|
234 | (1) |
|
6.2.3 Aldehydes, ketones, and carbamates |
|
|
234 | (2) |
|
6.2.4 Imines, acyl chlorides, and terminal alkynes |
|
|
236 | (1) |
|
6.2.5 Acetylenedicarboxylates, quinoline/isoquinoline, and terminal alkynes |
|
|
237 | (2) |
|
6.2.6 (Arylmethylene) cyclopropylcarbinols, terminal alkynes, and alcohols |
|
|
239 | (1) |
|
6.2.7 Amines, internal alkynes, and terminal alkynes |
|
|
240 | (2) |
|
6.2.8 Alkenes, boronic acid, and oxygen nucleophiles |
|
|
242 | (1) |
|
6.3 Gold-Catalyzed Three-Component Reactions/Tandem Cyclization |
|
|
243 | (4) |
|
6.3.1 Aldehydes, terminal alkynes, and amines/Cycloisomerization |
|
|
243 | (1) |
|
6.3.2 Glyoxylic acid, alkynes, and amines/Intramolecular cyclization |
|
|
244 | (2) |
|
6.3.3 Enantioselective [ 4 + 2] cycloaddition/Intramolecular hydroamination |
|
|
246 | (1) |
|
|
247 | (1) |
|
|
247 | (6) |
|
|
248 | (5) |
|
Chapter 7 Gold Catalysis on Tandem and Cascade Reactions |
|
|
253 | (22) |
|
|
|
253 | (1) |
|
|
254 | (9) |
|
|
263 | (3) |
|
|
266 | (1) |
|
|
266 | (1) |
|
|
266 | (1) |
|
|
267 | (1) |
|
|
268 | (1) |
|
|
269 | (1) |
|
7.10 Alkynyl Hydroxylamine |
|
|
270 | (1) |
|
|
271 | (4) |
|
|
271 | (4) |
|
Chapter 8 Cycloisomerization Reactions of 1, N-Enynes |
|
|
275 | (56) |
|
|
|
|
275 | (1) |
|
|
275 | (3) |
|
8.3 Gold-Catalyzed Cyclization of 1, n-Enynes |
|
|
278 | (53) |
|
8.3.1 Gold-catalyzed cycloisomerizations of 1, 6-enynes |
|
|
278 | (15) |
|
8.3.2 Gold-catalyzed cycloisomerizations and skeletal rearrangement of 1, 5-enynes |
|
|
293 | (16) |
|
8.3.3 Gold-catalyzed cycloisomerizations and skeletal rearrangement of 1, n-enynes (n > 6) |
|
|
309 | (2) |
|
8.3.4 Intermolecular reactions of alkynes with alkenes and [ 2 + 2] cycloadditions |
|
|
311 | (3) |
|
|
314 | (17) |
|
Chapter 9 Gold-Catalyzed Reactions of Propargylic Esters |
|
|
331 | (62) |
|
|
|
|
|
|
331 | (4) |
|
9.2 1,2-O-Acyl Migrations |
|
|
335 | (10) |
|
9.2.1 Scope and applications |
|
|
335 | (8) |
|
9.2.2 Intermolecular processes |
|
|
343 | (2) |
|
9.3 1,3-O-Acyl Migrations |
|
|
345 | (35) |
|
9.3.1 Intramolecular nucleophilic additions onto the gold-activated allenyl ester |
|
|
346 | (9) |
|
9.3.2 Allenyl esters as nucleophiles in allenyne systems |
|
|
355 | (7) |
|
9.3.3 Cycloadditions and electrocyclizations |
|
|
362 | (10) |
|
9.3.4 Access to unsaturated carbonyl derivatives from propargylic esters |
|
|
372 | (4) |
|
9.3.5 Access to (1, 3)-dienes from propargylic esters |
|
|
376 | (4) |
|
|
380 | (13) |
|
|
381 | (12) |
|
Chapter 10 Gold-Catalyzed Cross-Coupling Reactions |
|
|
393 | (20) |
|
|
|
393 | (1) |
|
10.2 Dual-Catalytic Gold and Palladium Cross-Coupling Reactions |
|
|
394 | (7) |
|
10.2.1 Mechanistic reaction design considerations |
|
|
394 | (1) |
|
10.2.2 Simultaneous activation: Gold-catalyzed cyclization initiates oxidative addition of palladium |
|
|
395 | (4) |
|
10.2.3 Tandem reactivity: Sonogashira-type cross-couplings with gold and palladium |
|
|
399 | (2) |
|
10.3 Fundamental Understanding through Stoichiometric Experiments |
|
|
401 | (7) |
|
10.3.1 Palladium-catalyzed cross-coupling of stoichiometric organogold reagents |
|
|
402 | (3) |
|
10.3.2 Mechanism: Single-step transmetalation |
|
|
405 | (1) |
|
|
406 | (2) |
|
|
408 | (1) |
|
10.4.1 Gold redox reactivity |
|
|
408 | (1) |
|
10.4.2 Dual-catalytic turnover strategies |
|
|
409 | (1) |
|
|
409 | (4) |
|
|
410 | (3) |
|
Chapter 11 Gold-Catalyzed Reactions: A Computational Approach |
|
|
413 | (32) |
|
|
|
|
413 | (2) |
|
11.2 Theoretical Considerations |
|
|
415 | (13) |
|
11.2.1 Relativistic effects |
|
|
415 | (3) |
|
11.2.2 Structure and bonding properties of the reactant complexes |
|
|
418 | (10) |
|
11.3 Mechanistic Considerations |
|
|
428 | (10) |
|
11.3.1 Alkyne activation and reactivity |
|
|
428 | (2) |
|
11.3.2 Key intermediates: Carbene or carbocation |
|
|
430 | (6) |
|
11.3.3 Other mechanistic considerations |
|
|
436 | (2) |
|
|
438 | (7) |
|
|
438 | (7) |
|
Chapter 12 Recent Developments in Asymmetric Catalysis |
|
|
445 | (56) |
|
|
|
|
12.1 Reactivity of Carbonyl- and Imine-Functionalized Derivatives |
|
|
448 | (6) |
|
12.2 Reactivity of Functionalized Alkenes |
|
|
454 | (6) |
|
12.2.1 Hydrogenation and protonation reactions |
|
|
454 | (1) |
|
12.2.2 Nucleophilic additions to alkenes or alkenyl intermediates |
|
|
455 | (5) |
|
12.3 Gold-Catalyzed Activation of Allenes |
|
|
460 | (12) |
|
12.3.1 Enantioselective addition of oxygen nucleophiles to allenes |
|
|
460 | (3) |
|
12.3.2 Enantioselective addition of nitrogen nucleophiles to allenes |
|
|
463 | (4) |
|
12.3.3 Enantioselective addition of carbon nucleophiles to allenes |
|
|
467 | (5) |
|
12.4 Gold-Catalyzed Activation of Alkynes |
|
|
472 | (20) |
|
12.4.1 Rearrangement of propargylic esters and reactivity of carbenoid intermediates |
|
|
472 | (5) |
|
12.4.2 Addition of carbon or heteroatom to alkynes |
|
|
477 | (5) |
|
12.4.3 Cycloisomerization reactions of enynes |
|
|
482 | (10) |
|
|
492 | (9) |
|
|
493 | (8) |
|
Chapter 13 Gold Catalysis in Natural Product Synthesis |
|
|
501 | (36) |
|
|
|
|
501 | (1) |
|
13.2 Addition of Heteroatoms |
|
|
502 | (21) |
|
13.2.1 Hydration of alkynes: Synthesis of ketones |
|
|
502 | (2) |
|
13.2.2 Intramolecular hydroalkoxylations |
|
|
504 | (4) |
|
|
508 | (3) |
|
13.2.4 Cyclization via pyrylium intermediates |
|
|
511 | (1) |
|
13.2.5 1,2- and 1,3-Acyl migration |
|
|
512 | (4) |
|
13.2.6 Hydrocarboxylation |
|
|
516 | (2) |
|
|
518 | (3) |
|
13.2.8 Rearrangements of N-Oxides |
|
|
521 | (2) |
|
|
523 | (5) |
|
13.3.1 The Conia-ene reaction |
|
|
523 | (2) |
|
13.3.2 Enyne-pinacol cascade reactions |
|
|
525 | (1) |
|
13.3.3 Formal [ 2 + 2 + 2] enyne/carbonyl cycloadditions |
|
|
526 | (1) |
|
13.3.4 Other cascade reactions |
|
|
526 | (2) |
|
13.4 Hydroarylation Reactions |
|
|
528 | (2) |
|
|
530 | (1) |
|
|
531 | (6) |
|
|
532 | (5) |
Index |
|
537 | |