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Gold Catalysis: An Homogeneous Approach Catalytic Science Series ed. [Kõva köide]

Edited by (Universite Cote D'azur, France), Edited by (Univ Of California, Berkeley, Usa)
  • Formaat: Hardback, 564 pages
  • Sari: Catalytic Science Series 13
  • Ilmumisaeg: 26-Aug-2014
  • Kirjastus: Imperial College Press
  • ISBN-10: 1848168527
  • ISBN-13: 9781848168527
Teised raamatud teemal:
  • Formaat: Hardback, 564 pages
  • Sari: Catalytic Science Series 13
  • Ilmumisaeg: 26-Aug-2014
  • Kirjastus: Imperial College Press
  • ISBN-10: 1848168527
  • ISBN-13: 9781848168527
Teised raamatud teemal:
Long considered catalitically inactive, gold now plays a central role in modern organic chemistry, and here scientists explain its use as a catalyst in methodologies that create carbon-carbon and carbon-heteroatom bonds. The topics include homogeneous gold-catalyzed oxidation and reduction reactions, the gold-catalyzed addition of a heteroatom nucleophile to a carbon-carbon multiple bond, gold-catalyzed multi-component reactions, gold catalysis on tandem and cascade reactions, gold-catalyzed reactions of propargylic esters, recent developments in asymmetric catalysis, and gold catalysis in natural products synthesis. Distributed in the US by World Scientific. Annotation ©2015 Ringgold, Inc., Portland, OR (protoview.com)

Research on designing new catalytic systems has been one of the most important fields in modern organic chemistry, and one reason for this is the predominant contribution of catalysis to the concepts of atom economy and green chemistry in the 21st century. Gold, considered catalytically inactive for a long time, is now a fascinating partner of modern chemistry, as scientists such as Bond, Haruta, Hutchings, Ito and Hayashi opened new perspectives for the whole synthetic chemist community. This book presents the major advances in homogeneous catalysis, emphasizing the methodologies that create carbon-carbon and carbon-heteroatom bonds, the applications that create diversity and synthesize natural products, and the recent advances and challenges in asymmetric catalysis and computational research.The Handbook of Homogeneous Gold Catalysis provides readers with in-depth information about gold-catalyzed reactions and presents several explanations for the scientific design of a catalyst. Readers will be able to understand the entire gold area and find solutions to problems in catalysis.Featuring prominent authors, who are experts in their respective fields, this is the first book dedicated to homogeneous gold chemistry.
Contributors xiii
Chapter 1 From Gold in Nature to Gold Catalysts
1(50)
Søren Kramer
Fabien Gagosz
1.1 The Gold Element: An Overview
1(4)
1.1.1 History of gold
1(1)
1.1.2 Abundance, production, and stocks
2(1)
1.1.3 Demand and supply
3(1)
1.1.4 Price
3(1)
1.1.5 General physical and chemical properties
4(1)
1.1.6 Applications
4(1)
1.2 History of Homogeneous Gold Catalysis
5(4)
1.3 General Reactivity of Electrophilic Gold Species
9(5)
1.4 Gold Catalysts
14(24)
1.4.1 Inorganic gold catalysts
16(3)
1.4.2 Gold complexes
19(15)
1.4.3 Chiral catalysts
34(4)
1.5 Conclusion
38(13)
References
40(11)
Chapter 2 Homogeneous Gold-Catalyzed Oxidation and Reduction Reactions
51(36)
Liming Zhang
2.1 Introduction
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)
2.5 Summary
80(1)
2.6 Acknowledgment
80(7)
References
81(6)
Chapter 3 Gold-Catalyzed Addition of Carbon Nucleophiles to C-C Multiple Bonds, Carbonyls, and other Electrophiles
87(50)
Bryon L. Simmons
Hong C. Shen
3.1 Introduction
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)
3.8 Conclusion
129(8)
References
130(7)
Chapter 4 Gold-Catalyzed Addition of Heteroatom Nucleophile to C--C Multiple Bond
137(38)
Naoki Asao
Naoya Hatakeyama
Yoshinori Yamamoto
4.1 Introduction
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)
4.3 Oxygen Nucleophiles
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)
4.4 Sulfur Nucleophiles
164(1)
4.5 Other Heteroatom Nucleophiles
165(1)
4.6 Conclusion
166(9)
References
166(9)
Chapter 5 Gold-Catalyzed Synthesis of Heterocycles
175(50)
Antonio Arcadi
5.1 Introduction
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)
5.9 Conclusions
215(10)
References
217(8)
Chapter 6 Gold-Catalyzed Multi-Component Reactions
225(28)
Rachid Skouta
Chao-Jun Li
6.1 Introduction
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)
6.4 Concluding Remarks
247(1)
6.5 Acknowledgments
247(6)
References
248(5)
Chapter 7 Gold Catalysis on Tandem and Cascade Reactions
253(22)
Rai-Shung Liu
7.1 Introduction
253(1)
7.2 Oxo Alkynes
254(9)
7.3 Oxodienes
263(3)
7.4 Iminoalkynes
266(1)
7.5 Aminoalkynes
266(1)
7.6 Nitroalkyne
266(1)
7.7 Alkynyl Nitrone
267(1)
7.8 Allenyl Acetals
268(1)
7.9 Epoxyalkynes
269(1)
7.10 Alkynyl Hydroxylamine
270(1)
7.11 Conclusion
271(4)
References
271(4)
Chapter 8 Cycloisomerization Reactions of 1, N-Enynes
275(56)
Nuria Huguet
Antonio M. Echavarren
8.1 Introduction
275(1)
8.2 Gold Complexes
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)
References
314(17)
Chapter 9 Gold-Catalyzed Reactions of Propargylic Esters
331(62)
Louis Fensterbank
Jean-Philippe Goddard
Max Malacria
Antoine Simonneau
9.1 Introduction
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)
9.4 Conclusion
380(13)
References
381(12)
Chapter 10 Gold-Catalyzed Cross-Coupling Reactions
393(20)
Suzanne A. Blum
10.1 Introduction
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)
10.3.3 Other metals
406(2)
10.4 Challenges
408(1)
10.4.1 Gold redox reactivity
408(1)
10.4.2 Dual-catalytic turnover strategies
409(1)
10.5 Outlook
409(4)
References
410(3)
Chapter 11 Gold-Catalyzed Reactions: A Computational Approach
413(32)
Elena Soriano
Jose Marco-Contelles
11.1 Introduction
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)
11.4 Acknowledgment
438(7)
References
438(7)
Chapter 12 Recent Developments in Asymmetric Catalysis
445(56)
Patrick Y. Toullec
Alexandre Pradal
Veronique Michelet
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)
12.5 Conclusion
492(9)
References
493(8)
Chapter 13 Gold Catalysis in Natural Product Synthesis
501(36)
Michael R. Gesinski
F. Dean Toste
13.1 Introduction
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)
13.2.3 Spiroketalization
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)
13.2.7 Hydroamination
518(3)
13.2.8 Rearrangements of N-Oxides
521(2)
13.3 Enyne Cyclizations
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)
13.5 Aldol Reactions
530(1)
13.6 Conclusion
531(6)
References
532(5)
Index 537