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Principles and Applications of Asymmetric Synthesis

Guo-Qiang Lin, Yue-Ming Li, Albert S.C. Chan

ISBNs: 0-471-40027-0 (Hardback); 0-471-22042-6 (Electronic)

PRINCIPLES AND

APPLICATIONS OF

ASYMMETRIC SYNTHESIS

PRINCIPLES AND

APPLICATIONS OF ASYMMETRIC SYNTHESIS

Guo-Qiang Lin

Yue-Ming Li

Albert S. C. Chan

A JOHN WILEY & SONS, INC., PUBLICATION

New York . Chichester . Weinheim . Brisbane . Singapore . Toronto

Designations used by companies to distinguish their products are often claimed as trademarks. In all instances where John Wiley & Sons, Inc., is aware of a claim, the product names appear in initial capital or all capital letters. Readers, however, should contact the appropriate companies for more complete information regarding trademarks and registration.

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This publication is designed to provide accurate and authoritative information in regard to the subject matter covered. It is sold with the understanding that the publisher is not engaged in rendering professional services. If professional advice or other expert assistance is required, the services of a competent professional person should be sought.

ISBN 0-471-22042-6

This title is also available in print as ISBN 0-471-40027-0.

For more information about Wiley products, visit our web site at www.Wiley.com.

Dedicated to Professors Chung-Kwong Poon and Wei-Shan Zhou

CONTENTS

Preface	xiii
Abbreviations	xv
1 Introduction	1

1.1The Signi®cance of Chirality and Stereoisomeric

	Discrimination		3
1.2	Asymmetry		7
	1.2.1	Conditions for Asymmetry	7
	1.2.2	Nomenclature	8
1.3	Determining Enantiomer Composition		16
	1.3.1	Measuring Speci®c Rotation	17
	1.3.2 The Nuclear Magnetic Resonance Method		19

1.3.3Some Other Reagents for Nuclear Magnetic

Resonance Analysis

1.3.4Determining the Enantiomer Composition of Chiral

	Glycols or Cyclic Ketones	24
1.3.5 Chromatographic Methods Using Chiral Columns		25
1.3.6 Capillary Electrophoresis with Enantioselective
	Supporting Electrolytes	28
1.4 Determining Absolute Con®guration		29
1.4.1	X-Ray Di¨raction Methods	30
1.4.2	Chiroptical Methods	32
1.4.3 The Chemical Interrelation Method		35
1.4.4	Prelog's Method	36
1.4.5	Horeau's Method	39

1.4.6Nuclear Magnetic Resonance Method for Relative

		Con®guration Determination	40
1.5	General Strategies for Asymmetric Synthesis		47
	1.5.1	``Chiron'' Approaches	48
	1.5.2	Acyclic Diastereoselective Approaches	49
	1.5.3	Double Asymmetric Synthesis	53
1.6	Examples of Some Complicated Compounds		56

1.7Some Common De®nitions in Asymmetric Synthesis and

Stereochemistry	62
1.8 References	65

vii

viii	CONTENTS
2 a-Alkylation and Catalytic Alkylation of Carbonyl Compounds			71
2.1	Introduction		71
2.2	Chirality Transfer		73
	2.2.1	Intra-annular Chirality Transfer	74
	2.2.2	Extra-annular Chirality Transfer	78
	2.2.3 Chelation-Enforced Intra-annular Chirality Transfer		79
2.3	Preparation of Quaternary Carbon Centers		98
2.4	Preparation of a-Amino Acids		103
2.5	Nucleophilic Substitution of Chiral Acetal		103

2.6Chiral Catalyst-Induced Aldehyde Alkylation: Asymmetric

Nucleophilic Addition

107

2.7Catalytic Asymmetric Additions of Dialkylzinc to Ketones:

	Enantioselective Formation of Tertiary Alcohols	118
2.8	Asymmetric Cyanohydrination	118
2.9	Asymmetric a-Hydroxyphosphonylation	124
2.10	Summary	127
2.11	References	127
3 Aldol and Related Reactions		135
3.1	Introduction	135
3.2	Substrate-Controlled Aldol Reaction	138

3.2.1Oxazolidones as Chiral Auxiliaries: Chiral Auxiliary-

Mediated Aldol-Type Reactions	138
3.2.2 Pyrrolidines as Chiral Auxiliaries	142
3.2.3 Aminoalcohols as the Chiral Auxiliaries	145
3.2.4 Acylsultam Systems as the Chiral Auxiliaries	148
3.2.5 a-Silyl Ketones	150
3.3 Reagent-Controlled Aldol Reactions	150

3.3.1	Aldol Condensations Induced by Chiral Boron
	Compounds	150
3.3.2	Aldol Reactions Controlled by Corey's Reagents	151

3.3.3Aldol Condensations Controlled by Miscellaneous

	Reagents	154
3.4 Chiral Catalyst-Controlled Asymmetric Aldol Reaction		155
3.4.1	Mukaiyama's System	155
3.4.2	Asymmetric Aldol Reactions with a Chiral
	Ferrocenylphosphine±Gold(I) Complex	159

3.4.3Asymmetric Aldol Reactions Catalyzed by Chiral

Lewis Acids

160

3.4.4Catalytic Asymmetric Aldol Reaction Promoted by

Bimetallic Catalysts: Shibasaki's System	163
3.5 Double Asymmetric Aldol Reactions	165

		CONTENTS	ix
3.6	Asymmetric Allylation Reactions		167
	3.6.1	The Roush Reaction	168
	3.6.2	The Corey Reaction	174
	3.6.3 Other Catalytic Asymmetric Allylation Reactions		175
3.7	Asymmetric Allylation and Alkylation of Imines		179
3.8	Other Types of Addition Reactions: Henry Reaction		186
3.9	Summary		188
3.10	References		188
4 Asymmetric Oxidations			195

4.1Asymmetric Epoxidation of Allylic Alcohols: Sharpless

	Epoxidation	195
	4.1.1 The Characteristics of Sharpless Epoxidation	197
	4.1.2 Mechanism	199
	4.1.3 Modi®cations and Improvements of Sharpless
	Epoxidation	200
4.2	Selective Opening of 2,3-Epoxy Alcohols	204
	4.2.1 External Nucleophilic Opening of 2,3-Epoxy Alcohols	205
	4.2.2 Opening by Intramolecular Nucleophiles	207
	4.2.3 Opening by Metallic Hydride Reagents	209
	4.2.4 Opening by Organometallic Compounds	210
	4.2.5 Payne Rearrangement and Ring-Opening Processes	211
	4.2.6 Asymmetric Desymmetrization of meso-Epoxides	214
4.3	Asymmetric Epoxidation of Symmetric Divinyl Carbinols	217
4.4	Enantioselective Dihydroxylation of Ole®ns	221
4.5	Asymmetric Aminohydroxylation	232
4.6	Epoxidation of Unfunctionalized Ole®ns	237

4.6.1Catalytic Enantioselective Epoxidation of Simple

Ole®ns by Salen Complexes

237

4.6.2Catalytic Enantioselective Epoxidation of Simple

Ole®ns by Porphyrin Complexes

243

4.6.3Chiral Ketone±Catalyzed Asymmetric Oxidation of

Unfunctionalized Ole®ns	244
4.7 Catalytic Asymmetric Epoxidation of Aldehydes	249

4.8Asymmetric Oxidation of Enolates for the Preparation of

	Optically Active a-Hydroxyl Carbonyl Compounds		250
	4.8.1	Substrate-Controlled Reactions	251
	4.8.2	Reagent-Controlled Reactions	252
4.9	Asymmetric Aziridination and Related Reactions		255
	4.9.1	Asymmetric Aziridination	255
	4.9.2 Regioselective Ring Opening of Aziridines		257
4.10	Summary		260
4.11	References		261

xCONTENTS

5 Asymmetric Diels-Alder and Other Cyclization Reactions			267
5.1	Chiral Dienophiles		268
	5.1.1	Acrylate	269
	5.1.2	a; b-Unsaturated Ketone	270
	5.1.3	Chiral a; b-Unsubstituted N-Acyloxazolidinones	273
	5.1.4 Chiral Alkoxy Iminium Salt		273
	5.1.5 Chiral Sul®nyl-Substituted Compounds as
		Dienophiles	277
5.2	Chiral Dienes		277
5.3	Double Asymmetric Cycloaddition		278
5.4	Chiral Lewis Acid Catalysts		279
	5.4.1	Narasaka's Catalyst	280
	5.4.2	Chiral Lanthanide Catalyst	282
	5.4.3	Bissulfonamides (Corey's Catalyst)	282
	5.4.4 Chiral Acyloxy Borane Catalysts		283
	5.4.5 Brùnsted Acid±Assisted Chiral Lewis Acid Catalysts		285
	5.4.6	Bis(Oxazoline) Catalysts	287
	5.4.7 Amino Acid Salts as Lewis Acids for Asymmetric
		Diels-Alder Reactions	289
5.5	Hetero Diels-Alder Reactions		290
	5.5.1	Oxo Diels-Alder Reactions	290
	5.5.2	Aza Diels-Alder Reactions	296

5.6Formation of Quaternary Stereocenters Through Diels-Alder

	Reactions	301
5.7	Intramolecular Diels-Alder Reactions	301
5.8	Retro Diels-Alder Reactions	306
5.9	Asymmetric Dipolar Cycloaddition	308
5.10	Asymmetric Cyclopropanation	313
	5.10.1 Transition Metal Complex±Catalyzed
	Cyclopropanations	314
	5.10.2 The Catalytic Asymmetric Simmons-Smith Reaction	319
5.11	Summary	322
5.12	References	323

6Asymmetric Catalytic Hydrogenation and Other Reduction

Reactions	331
6.1 Introduction	331

6.1.1Chiral Phosphine Ligands for Homogeneous

	Asymmetric Catalytic Hydrogenation	332
6.1.2	Asymmetric Catalytic Hydrogenation of CbC Bonds	334
6.2 Asymmetric Reduction of Carbonyl Compounds		355
6.2.1	Reduction by BINAL±H	356

	CONTENTS	xi
	6.2.2 Transition Metal±Complex Catalyzed Hydrogenation
	of Carbonyl Compounds	359
	6.2.3 The Oxazaborolidine Catalyst System	367
6.3	Asymmetric Reduction of Imines	373
6.4	Asymmetric Transfer Hydrogenation	377
6.5	Asymmetric Hydroformylation	384
6.6	Summary	388
6.7	References	389

7Applications of Asymmetric Reactions in the Synthesis of Natural

Products			397
7.1	The Synthesis of Erythronolide A		397
7.2	The Synthesis of 6-Deoxyerythronolide		400
7.3	The Synthesis of Rifamycin S		403
	7.3.1 Kishi's Synthesis in 1980		404
	7.3.2 Kishi's Synthesis in 1981		408
	7.3.3	Masamune's Synthesis	409
7.4	The Synthesis of Prostaglandins		412
	7.4.1	Three-Component Coupling	414
	7.4.2 Synthesis of the o-Side Chain		415

7.4.3The Enantioselective Synthesis of (R)-4-Hydroxy-2-

Cyclopentenone

417

7.5The Total Synthesis of TaxolÐA Challenge and Opportunity for Chemists Working in the Area of

	Asymmetric Synthesis		418
	7.5.1 Synthesis of Baccatin III, the Polycyclic Part of Taxol		419
	7.5.2 Asymmetric Synthesis of the Taxol Side Chain		442
7.6	Summary		445
7.7	References		446
8 Enzymatic Reactions and Miscellaneous Asymmetric Syntheses			451
8.1	Enzymatic and Related Processes		451
	8.1.1	Lipase/Esterase-Catalyzed Reactions	452
	8.1.2	Reductions	454
	8.1.3	Enantioselective Microbial Oxidation	455
	8.1.4 Formation of C±C Bond		456
	8.1.5 Biocatalysts from Cultured Plant Cells		458
8.2	Miscellaneous Methods		458

8.2.1Asymmetric Synthesis Catalyzed by Chiral

	Ferrocenylphosphine Complex	458
8.2.2	Asymmetric Hydrosilylation of Ole®ns	459
8.2.3	Synthesis of Chiral Biaryls	460

xii CONTENTS

8.2.4 The Asymmetric Kharasch Reaction

464

8.2.5Optically Active Lactones from Metal-Catalyzed Baeyer-Villiger±Type Oxidations Using Molecular

Oxygen as the Oxidant

465

8.2.6Recent Progress in Asymmetric Wittig-Type

	Reactions	466
8.2.7	Asymmetric Reformatsky Reactions	469
8.2.8	Catalytic Asymmetric Wacker Cyclization	470

8.2.9Palladium-Catalyzed Asymmetric Alkenylation of

	Cyclic Ole®ns	471
8.2.10	Intramolecular Enyne Cyclization	474
8.2.11	Asymmetric Darzens Reaction	475
8.2.12	Asymmetric Conjugate Addition	476
8.2.13	Asymmetric Synthesis of Fluorinated Compounds	481
8.3 New Concepts in Asymmetric Reaction		484
8.3.1	Ti Catalysts from Self-Assembly Components	484
8.3.2	Desymmetrization	486
8.3.3	Cooperative Asymmetric Catalysis	486

8.3.4Stereochemical Nonlinear E¨ects in Asymmetric

	Reaction	492
8.3.5	Chiral Poisoning	494
8.3.6	Enantioselective Activation and Induced Chirality	496

8.4Chiral Ampli®cation, Chiral Autocatalysis, and the Origin of

	Natural Chirality	499
8.5	Summary	501
8.6	References	501
Index		509

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