Stereoselectivity in Synthesis

Many chemicals are found in "right-" and "left-handed" forms that may react differently in the body. In planning a synthesis, chemists must know how to select the best method for making the preferred form of a chemical. This book shows how to choose the best method for a given synthesis. It provides readers with a thorough understanding of stereoselectivity in organic and medicinal chemistry as well as the pharmaceutical, agricultural, and food industries.

TSE-LOK HO is Professor of Organic Chemistry at National Chiao Tung University in Taiwan. His research interests are in organic synthesis, including total synthesis of natural products and methodology. He has written 12 books, including, most recently, Stereoselectivity in Synthesis, available from Wiley. Dr. Ho holds degrees from National Taiwan University and the University of New Brunswick, Canada.

Preface

xi

General Abbreviations

xiii

Some Fundamental Concepts

1

(8)

Configurations

1

(2)

Conformations

3

(3)

Thrusts of Substrate-Induced Stereoselectivity

6

(1)

Double and Triple Stereodifferentiations

6

(1)

References

7

(2)

1,2-Stereoinduction

9

(26)

Alkylations

9

(6)

Additions

15

(7)

Cycloadditions

22

(5)

Other Reactions

27

(3)

Self-Imposed 1,2-Stereoinductions

30

(2)

References

32

(3)

1,3-Stereoinduction

35

(52)

Consequences of 1,3-Interactions in a Six-Centered Array

35

(15)

Other 1,3-Stereoinductions

50

(16)

A1.3-Strain and Reactivity

66

(16)

References

82

(5)

Stereoinduction at Long Distances

87

(19)

1,4-Stereoinduction

87

(8)

1,5-Stereoinduction

95

(5)

Remote Stereoinduction

100

(4)

References

104

(2)

Group Directed Reactions and Chelation Effects

106

(43)

Directed Oxidations

106

(8)

Epoxidation of Alkenes with Peracids

106

(2)

Metal-Catalyzed Epoxidations

108

(4)

Dihydroxylations

112

(1)

Hydration via Hydroboration

113

(1)

Directed Reductions

114

(9)

Reduction of Double Bonds

114

(4)

Metal Hydride Reduction of C=X Bonds

118

(5)

Directed C-C Bond Formation

123

(15)

Simmons-Smith Reaction

123

(3)

Alkylations via Chelates

126

(12)

Intramolecular Reactions

138

(4)

References

142

(7)

Conformational Effects

149

(42)

Group Anchoring

149

(12)

Nonbonded Interactions

161

(9)

Chair Versus Boat Conformation

170

(8)

Macrocyclic Systems

178

(6)

s-cis versus s-trans Conformations

184

(2)

References

186

(5)

Topographical and Template Effects

191

(54)

Topographical Influence of Steric Courses

191

(31)

Condensed Ring Systems

191

(20)

Bridged Ring Systems

211

(11)

Template Effects

222

(16)

π-Stacking

223

(3)

Steric Bulk

226

(5)

Ligated Metallic Components for Diastereofacial Selection

231

(7)

References

238

(7)

Steric, Electrostatic, and Stereoelectronic Effects

245

(42)

Steric Effects

245

(4)

Electrostatic Effects

249

(3)

Stereoelectronic Effects

252

(23)

Stereoelectronic Effects in Carbocycles

252

(13)

Stereoelectronic Effects in Heterocycles

265

(10)

Pericyclic Reactions

275

(8)

References

283

(4)

Thermodynamic Control and Kinetic Trapping

287

(40)

Configuration Inversion by Equilibration

287

(18)

Configuration Inversion by Other Methods

305

(1)

Kinetic Trapping

306

(8)

Self-Regulation of Configurations

314

(7)

Alkene Isomerization

321

(2)

References

323

(4)

Index

327

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Stereoselectivity in Synthesis

Summary

Author Biography

Table of Contents

Supplemental Materials