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Modern Enolate Chemistry: From Preparation to Applications in Asymmetric Synthesis

Modern Enolate Chemistry: From Preparation to Applications in Asymmetric Synthesis

Manfred Braun

ISBN: 978-3-527-67106-9

Nov 2015

456 pages

Description

Authored by one of the world?s leading synthetic chemists in the field, this reference presents modern enolate chemistry with an emphasis on metal O-enolates in asymmetric synthesis.
While great care is taken to cover novel, successful concepts, such classical methods as the famous Evans enolates are equally highlighted. Throughout the book representative reaction procedures are presented, thus helping readers to find the best solution for their own synthetic problem.
Of high interest to synthetic chemists in academia, as well as the pharmaceuticals, agrochemicals and fine chemicals industries.

Preface VII

1 Introductory Remarks 1

References 7

2 General Methods for the Preparation of Enolates 11

2.1 Enolate Formation by Deprotonation 11

2.2 Enolate Formation by Conjugate Addition to α,β-Unsaturated Carbonyl Compounds 51

2.3 Alkali Metal Enolates by Cleavage of Enol Acetates or Silyl Enol Ethers 60

2.4 Enolates from Ketenes and Organolithium Compounds 62

2.5 Enolates from α-Halogen-Substituted Carbonyl Compounds by Halogen–Metal Exchange 63

2.6 Formation of Enolates by Transmetallation 65

2.7 Enolates by Miscellaneous Methods 70

References 72

3 Structures of Enolates 83

3.1 Enolates of Alkali and Alkaline Earth Metals 83

3.2 Enolates of Other Main Group Metals 98

3.3 Transition Metal Enolates 100

References 109

4 Enolates with Chiral Auxiliaries in Asymmetric Syntheses 115

4.1 Auxiliary-Based Alkylation of Enolates 116

4.2 Auxiliary-Based Arylation of Enolates 144

4.3 Auxiliary-Based Aldol, Vinylogous Aldol, and Reformatsky Reactions 147

4.4 Auxiliary-Based Mannich Reactions and Ester Enolate-Imine Condensations 202

4.5 Auxiliary-Based Conjugate Additions 214

4.6 Auxiliary-Based Oxidation of Enolates 227

References 242

5 Enolates in Asymmetric Catalysis 257

5.1 Enantioselective Catalysis in Alkylations and Allylations of Enolates 257

5.2 Enantioselective Catalysis for Enolate Arylation 300

5.3 Catalytic, Enantioselective Aldol, Vinylogous Aldol, and Reformatsky Reactions 309

5.4 Catalytic Enantioselective Mannich Reactions, Ester Enolate–Imine Condensations, and Imine Reformatsky Reactions 352

5.5 Catalytic Enantioselective Conjugate Additions 369

5.6 Enantioselective Protonation of Enolates 385

5.7 Enantioselective Oxidation of Enolates 394

References 408

List of Procedures 423

Index 437