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Enantioselection in Asymmetric Catalysis [Kõva köide]

(Tohoku University, Sendai, Japan),
  • Formaat: Hardback, 234 pages, kõrgus x laius: 234x156 mm, kaal: 635 g, 3 Tables, black and white; 25 Illustrations, color; 192 Illustrations, black and white
  • Ilmumisaeg: 07-Nov-2016
  • Kirjastus: CRC Press Inc
  • ISBN-10: 1498726542
  • ISBN-13: 9781498726542
Teised raamatud teemal:
Enantioselection in Asymmetric CatalysisSuurem pilt
  • Formaat: Hardback, 234 pages, kõrgus x laius: 234x156 mm, kaal: 635 g, 3 Tables, black and white; 25 Illustrations, color; 192 Illustrations, black and white
  • Ilmumisaeg: 07-Nov-2016
  • Kirjastus: CRC Press Inc
  • ISBN-10: 1498726542
  • ISBN-13: 9781498726542
Teised raamatud teemal:
Püsilink: https://www.kriso.ee/db/9781498726542.html
Märksõnad:

The field of asymmetric catalysis is currently one of the hottest areas in chemistry. This unique book focuses on the mechanism of enantioselectivity in asymmetric catalysis, rather than asymmetric catalysis from the synthetic view. It describes reliable, experimentally and computationally supported mechanisms, and discusses the danger of so-called "plausible" or "accepted" mechanisms leading to wrong conclusions. It draws parallels to enzymatic catalysis in biochemistry, and examines in detail the physico-chemical aspects of enantioselective catalysis.

Introduction ix
Authors xi
Chapter 1 Transition metal-catalyzed hydrogenation
1(132)
1.1 Rh-catalyzed asymmetric hydrogenation of activated olefins
1(67)
1.1.1 Overview
1(1)
1.1.2 Asymmetric hydrogenation catalyzed by Rh--diphosphine ligands
1(1)
1.1.2.1 Resting state of the catalytic cycle: Formation of the catalyst--substrate complexes
1(7)
1.1.2.2 Activation of H2
8(4)
1.1.2.3 Formation of solvate dihydrides
12(3)
1.1.2.4 Oxidative addition to chelate catalyst--substrate complexes
15(7)
1.1.2.5 Reactions of solvate dihydrides with prochiral substrates
22(11)
1.1.2.6 Catalytic cycle and enantioselective step
33(4)
1.1.2.7 Process of enantioselection
37(17)
1.1.2.8 Sense of enantioselection and the relative size of substituents
54(8)
1.1.3 Catalysis with rhodium complexes of monophosphines
62(3)
1.1.4 Conclusions
65(3)
1.2 Ru-catalyzed asymmetric hydrogenation and transfer hydrogenation of ketones
68(26)
1.2.1 Overview
68(3)
1.2.2 A Brief Critical Overview of Experimental and Computational Techniques Used in the Early Mechanistic Studies of 1 and 2
71(1)
1.2.2.1 The characteristic time and sensitivity of NMR spectroscopy
71(1)
1.2.2.2 Kinetics
71(2)
1.2.2.3 Computations in the gas-phase
73(1)
1.2.3 Progress of the reaction mechanism with 1 and 2
74(11)
1.2.4 The origin of the enantioselectivity
85(4)
1.2.5 Unresolved problems
89(1)
1.2.5.1 Reaction mechanism
89(3)
1.2.5.2 Enantioselectivity
92(2)
1.3 Ir-catalyzed asymmetric hydrogenation of C=C and C=N bonds
94(10)
1.3.1 Overview
94(1)
1.3.2 Catalytic cycle and intermediates
94(3)
1.3.3 Mechanism of enantioselection
97(1)
1.3.3.1 Simple olefins
98(2)
1.3.3.2 Imines
100(1)
1.3.3.3 Heterocycles
101(3)
1.3.4 Conclusion
104(1)
1.4 Pd-catalyzed asymmetric hydrogenation of indoles
104(29)
1.4.1 Overview
104(1)
1.4.2 Catalytic cycle
105(1)
1.4.3 Enantioselectivity
106(2)
References
108(25)
Chapter 2 Other enantioselective reactions catalyzed by transition metals
133(50)
2.1 Enantioselective reactions catalyzed by bifunctional Ru and Ir complexes
133(10)
2.1.1 Mechanism of the Michael addition catalyzed by bifunctional Ru catalysts
133(2)
2.1.2 Mechanism of C--C and C--N bond forming reactions catalyzed by bifunctional Ir catalysts
135(8)
2.2 Rh-catalyzed stereoselective isomerization of tert-cyclobutanols into chiral indanoles
143(4)
2.2.1 Overview
143(1)
2.2.2 Catalytic cycle
144(3)
2.3 Os-catalyzed asymmetric dihydroxylation (Sharpless reaction)
147(5)
2.3.1 Overview
147(2)
2.3.2 Catalytic cycle
149(1)
2.3.3 Enantioselectivity
149(3)
2.4 Pd- and Rh-catalyzed conjugate additions of arylboronic acids to enones and nitrostyrenes (Hayashi--Miyaura reaction)
152(6)
2.4.1 Overview
152(1)
2.4.2 Catalytic cycle
152(2)
2.4.3 Catalytic cycle (M = Rh, Scheme 2.12)
154(1)
2.4.4 Origin of enantioselectivity (M = Pd)
155(2)
2.4.5 Origin of enantioselectivity (M = Rh)
157(1)
2.5 Rh-catalyzed asymmetric hydroboration of vinylarenes
158(6)
2.5.1 Overview
158(2)
2.5.2 Catalytic cycle
160(1)
2.5.3 Enantioselectivity
161(3)
2.6 Mechanism of autoamplifying Soai reaction
164(19)
2.6.1 Introduction
164(2)
2.6.2 Studies of the reaction pool of Soai reaction
166(2)
2.6.3 Structure of the catalyst and computations of the catalytic cycle of Soai reaction
168(4)
References
172(11)
Chapter 3 Mechanism of enantioselection in organocatalytic reactions
183(42)
3.1 Phosphoric acids
183(9)
3.1.1 Asymmetric allylboration
183(1)
3.1.2 Kinetic resolution in Robinson-type cyclization
184(1)
3.1.3 Friedel--Crafts alkylation of indoles with nitroalkenes
185(3)
3.1.4 Petasis--Ferrier-type rearrangement
188(2)
3.1.5 Enantioselective indole aza-Claisen rearrangement
190(1)
3.1.6 Asymmetric thiocarboxylysis of meso-epoxide
190(2)
3.1.7 Asymmetric sulfoxidation reaction
192(1)
3.2 Cinchona alkaloids
192(9)
3.2.1 Asymmetric olefin isomerization
194(1)
3.2.2 Friedel--Crafts alkylation of indoles with α, β-unsaturated ketones
195(3)
3.2.3 Conjugate addition of dimethyl malonate to β-nitrostyrene
198(1)
3.2.4 Fluorination of cyclic ketones
199(1)
3.2.5 Phase-transfer-catalyzed alkylation reaction
200(1)
3.3 Urea and thiourea-based catalysts
201(11)
3.3.1 Catalytic Strecker reaction
202(1)
3.3.2 Michael addition reactions
203(2)
3.3.3 Enantioselective decarboxylative protonation
205(2)
3.3.4 Henry reaction
207(2)
3.3.5 α-Hydroxylation of β-ketoesters
209(3)
3.4 N-Protonated chiral oxazaborolidine
212(2)
3.4.1 C--C insertion reaction
212(2)
3.5 FLP-catalyzed asymmetric hydrogenation of imines and enamines
214(11)
3.5.1 Overview
214(2)
3.5.2 Catalytic cycle
216(1)
3.5.3 Enantioselectivity
216(2)
References
218(7)
Conclusions 225(4)
Index 229
Ilya Gridnev is an associate professor at Tohoku University, Sendai, Japan. Pavel A. Dub is a J. Robert Oppenheimer postdoctoral fellow at Los Alamos National Laboratory, New Mexico, USA.