Principles and Applications of Asymmetric Synthesis

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

• ISBN13: 9780471400271
• ISBN10: 0471400270
• Edition: 1st
• Format: Hardcover
• Copyright: 2001-02-21
• Publisher: Wiley-Interscience

Summary

Asymmetric synthesis remains a challenge to practicing scientists as the need for enantiomerically pure or enriched compounds continues to increase. Over the last decade, a large amount of literature has been published in this field. Principles and Applications of Asymmetric Synthesis consolidates and evaluates the most useful methodologies into a one-volume resource for the convenience of practicing scientists and students. Authored by internationally renowned scientists in the field, this reliable reference covers more than 450 reactions and includes important stoichiometric as well as catalytic asymmetric reactions. The first chapter reviews the basic principles, common nomenclature, and analytical methods, and the remainder of the book is organized according to reaction type. The text examines such topics as: Carbon-carbon bond formations involving carbonyls, enamines, imines, and enolates Asymmetric C-O bond formations including epoxidation, dihydroxylation, and aminohydroxylation Asymmetric synthesis using the Diels-Alder reaction and other cyclizations Applications to the total synthesis of natural products Use of enzymes in asymmetric synthesis Practicing chemists in the pharmaceutical, fine chemical, and agricultural professions as well as graduate students will find that Principles and Applications of Asymmetric Synthesis affords comprehensive and current coverage.

Author Biography

GUO-QIANG LIN, YUE-MING LI, and ALBERT S. C. CHAN are all professors in the Department of Chemical Technology at The Hong Kong Polytechnic University, Hong Kong, China.

Table of Contents

Preface	xiii
Abbreviations	xv
Introduction	1	(70)
The Significance of Chirality and Stereoisomeric Discrimination	3	(4)
Asymmetry	7	(9)
Conditions for Asymmetry	7	(1)
Nomenclature	8	(8)
Determining Enantiomer Composition	16	(13)
Measuring Specific Rotation	17	(2)
The Nuclear Magnetic Resonance Method	19	(4)
Some Other Reagents for Nuclear Magnetic Resonance Analysis	23	(1)
Determining the Enantiomer Composition of Chiral Glycols or Cyclic Ketones	24	(1)
Chromatographic Methods Using Chiral Columns	25	(3)
Capillary Electrophoresis with Enantioselective Supporting Electrolytes	28	(1)
Determining Absolute Configuration	29	(18)
X-Ray Diffraction Methods	30	(2)
Chiroptical Methods	32	(3)
The Chemical Interrelation Method	35	(1)
Prelog's Method	36	(3)
Horeau's Method	39	(1)
Nuclear Magnetic Resonance Method for Relative Configuration Determination	40	(7)
General Strategies for Asymmetric Synthesis	47	(9)
``Chiron'' Approaches	48	(1)
Acyclic Diastereoselective Approaches	49	(4)
Double Asymmetric Synthesis	53	(3)
Examples of Some Complicated Compounds	56	(6)
Some Common Definitions in Asymmetric Synthesis and Stereochemistry	62	(3)
References	65	(6)
α-Alkylation and Catalytic Alkylation of Carbonyl Compounds	71	(64)
Introduction	71	(2)
Chirality Transfer	73	(25)
Intra-annular Chirality Transfer	74	(4)
Extra-annular Chirality Transfer	78	(1)
Chelation-Enforced Intra-annular Chirality Transfer	79	(19)
Preparation of Quaternary Carbon Centers	98	(5)
Preparation of α-Amino Acids	103	(1)
Nucleophilic Substitution of Chiral Acetal	103	(4)
Chiral Catalyst-Induced Aldehyde Alkylation: Asymmetric Nucleophilic Addition	107	(11)
Catalytic Asymmetric Additions of Dialkylzinc to Ketones: Enantioselective Formation of Tertiary Alcohols	118	(1)
Asymmetric Cyanohydrination	118	(6)
Asymmetric α-Hydroxyphosphonylation	124	(3)
Summary	127	(1)
References	127	(8)
Aldol and Related Reactions	135	(60)
Introduction	135	(3)
Substrate-Controlled Aldol Reaction	138	(12)
Oxazolidones as Chiral Auxiliaries: Chiral Auxiliary-Mediated Aldol-Type Reactions	138	(4)
Pyrrolidines as Chiral Auxiliaries	142	(3)
Aminoalcohols as the Chiral Auxiliaries	145	(3)
Acylsultam Systems as the Chiral Auxiliaries	148	(2)
α-Silyl Ketones	150	(1)
Reagent-Controlled Aldol Reactions	150	(5)
Aldol Condensations Induced by Chiral Boron Compounds	150	(1)
Aldol Reactions Controlled by Corey's Reagents	151	(3)
Aldol Condensations Controlled by Miscellaneous Reagents	154	(1)
Chiral Catalyst-Controlled Asymmetric Aldol Reaction	155	(10)
Mukaiyama's System	155	(4)
Asymmetric Aldol Reactions with a Chiral Ferrocenylphosphine-Gold(I) Complex	159	(1)
Asymmetric Aldol Reactions Catalyzed by Chiral Lewis Acids	160	(3)
Catalytic Asymmetric Aldol Reaction Promoted by Bimetallic Catalysts: Shibasaki's System	163	(2)
Double Asymmetric Aldol Reactions	165	(2)
Asymmetric Allylation Reactions	167	(12)
The Roush Reaction	168	(6)
The Corey Reaction	174	(1)
Other Catalytic Asymmetric Allylation Reactions	175	(4)
Asymmetric Allylation and Alkylation of Imines	179	(7)
Other Types of Addition Reactions: Henry Reaction	186	(2)
Summary	188	(1)
References	188	(7)
Asymmetric Oxidations	195	(72)
Asymmetric Epoxidation of Allylic Alcohols: Sharpless Epoxidation	195	(9)
The Characteristics of Sharpless Epoxidation	197	(2)
Mechanism	199	(1)
Modifications and Improvements of Sharpless Epoxidation	200	(4)
Selective Opening of 2,3-Epoxy Alcohols	204	(13)
External Nucleophilic Opening of 2,3-Epoxy Alcohols	205	(2)
Opening by Intramolecular Nucleophiles	207	(2)
Opening by Metallic Hydride Reagents	209	(1)
Opening by Organometallic Compounds	210	(1)
Payne Rearrangement and Ring-Opening Processes	211	(3)
Asymmetric Desymmetrization of meso-Epoxides	214	(3)
Asymmetric Epoxidation of Symmetric Divinyl Carbinols	217	(4)
Enantioselective Dihydroxylation of Olefins	221	(11)
Asymmetric Aminohydroxylation	232	(5)
Epoxidation of Unfunctionalized Olefins	237	(12)
Catalytic Enantioselective Epoxidation of Simple Olefins by Salen Complexes	237	(6)
Catalytic Enantioselective Epoxidation of Simple Olefins by Porphyrin Complexes	243	(1)
Chiral Ketone-Catalyzed Asymmetric Oxidation of Unfunctionalized Olefins	244	(5)
Catalytic Asymmetric Epoxidation of Aldehydes	249	(1)
Asymmetric Oxidation of Enolates for the Preparation of Optically Active α-Hydroxyl Carbonyl Compounds	250	(5)
Substrate-Controlled Reactions	251	(1)
Reagent-Controlled Reactions	252	(3)
Asymmetric Aziridination and Related Reactions	255	(5)
Asymmetric Aziridination	255	(2)
Regioselective Ring Opening of Aziridines	257	(3)
Summary	260	(1)
References	261	(6)
Asymmetric Diels-Alder and Other Cyclization Reactions	267	(64)
Chiral Dienophiles	268	(9)
Acrylate	269	(1)
α,β-Unsaturated Ketone	270	(3)
Chiral α,β-Unsubstituted N-Acyloxazolidinones	273	(1)
Chiral Alkoxy Iminium Salt	273	(4)
Chiral Sulfinyl-Substituted Compounds as Dienophiles	277	(1)
Chiral Dienes	277	(1)
Double Asymmetric Cycloaddition	278	(1)
Chiral Lewis Acid Catalysts	279	(11)
Narasaka's Catalyst	280	(2)
Chiral Lanthanide Catalyst	282	(1)
Bissulfonamides (Corey's Catalyst)	282	(1)
Chiral Acyloxy Borane Catalysts	283	(2)
Bronsted Acid--Assisted Chiral Lewis Acid Catalysts	285	(2)
Bis(Oxazoline) Catalysts	287	(2)
Amino Acid Salts as Lewis Acids for Asymmetric Diels-Alder Reactions	289	(1)
Hetero Diels-Alder Reactions	290	(11)
Oxo Diels-Alder Reactions	290	(6)
Aza Diels-Alder Reactions	296	(5)
Formation of Quaternary Stereocenters Through Diels-Alder Reactions	301	(1)
Intramolecular Diels-Alder Reactions	301	(5)
Retro Diels-Alder Reactions	306	(2)
Asymmetric Dipolar Cycloaddition	308	(5)
Asymmetric Cyclopropanation	313	(9)
Transition Metal Complex--Catalyzed Cyclopropanations	314	(5)
The Catalytic Asymmetric Simmons-Smith Reaction	319	(3)
Summary	322	(1)
References	323	(8)
Asymmetric Catalytic Hydrogenation and Other Reduction Reactions	331	(66)
Introduction	331	(24)
Chiral Phosphine Ligands for Homogeneous Asymmetric Catalytic Hydrogenation	332	(2)
Asymmetric Catalytic Hydrogenation of C=C Bonds	334	(21)
Asymmetric Reduction of Carbonyl Compounds	355	(18)
Reduction by Binal-H	356	(3)
Transition Metal-Complex Catalyzed Hydrogenation of Carbonyl Compounds	359	(8)
The Oxazaborolidine Catalyst System	367	(6)
Asymmetric Reduction of Imines	373	(4)
Asymmetric Transfer Hydrogenation	377	(7)
Asymmetric Hydroformylation	384	(4)
Summary	388	(1)
References	389	(8)
Applications of Asymmetric Reactions in the Synthesis of Natural Products	397	(54)
The Synthesis of Erythronolide A	397	(3)
The Synthesis of 6-Deoxyerythronolide	400	(3)
The Synthesis of Rifamycin S	403	(9)
Kishi's Synthesis in 1980	404	(4)
Kishi's Synthesis in 1981	408	(1)
Masamune's Synthesis	409	(3)
The Synthesis of Prostaglandins	412	(6)
Three-Component Coupling	414	(1)
Synthesis of the ω-Side Chain	415	(2)
The Enantioselective Synthesis of (R)-4-Hydroxy-2-Cyclopentenone	417	(1)
The Total Synthesis of Taxol--A Challenge and Opportunity for Chemists Working in the Area of Asymmetric Synthesis	418	(27)
Synthesis of Baccatin III, the Polycyclic Part of Taxol	419	(23)
Asymmetric Synthesis of the Taxol Side Chain	442	(3)
Summary	445	(1)
References	446	(5)
Enzymatic Reactions and Miscellaneous Asymmetric Syntheses	451	(58)
Enzymatic and Related Processes	451	(7)
Lipase/Esterase-Catalyzed Reactions	452	(2)
Reductions	454	(1)
Enantioselective Microbial Oxidation	455	(1)
Formation of C-C Bond	456	(2)
Biocatalysts from Cultured Plant Cells	458	(1)
Miscellaneous Methods	458	(26)
Asymmetric Synthesis Catalyzed by Chiral Ferrocenylphosphine Complex	458	(1)
Asymmetric Hydrosilyation of Olefins	459	(1)
Synthesis of Chiral Biaryls	460	(4)
The Asymmetric Kharasch Reaction	464	(1)
Optically Active Lactones from Metal-Catalyzed Baeyer-Villiger--Type Oxidations Using Molecular Oxygen as the Oxidant	465	(1)
Recent Progress in Asymmetric Wittig-Type Reactions	466	(3)
Asymmetric Reformatsky Reactions	469	(1)
Catalytic Asymmetric Wacker Cyclization	470	(1)
Palladium-Catalyzed Asymmetric Alkenylation of Cyclic Olefins	471	(3)
Intramolecular Enyne Cyclization	474	(1)
Asymmetric Darzens Reaction	475	(1)
Asymmetric Conjugate Addition	476	(5)
Asymmetric Synthesis of Fluorinated Compounds	481	(3)
New Concepts in Asymmetric Reaction	484	(15)
Ti Catalysts from Self-Assembly Components	484	(2)
Desymmetrization	486	(1)
Cooperative Asymmetric Catalysis	486	(6)
Sterochemical Nonlinear Effects in Asymmetric Reaction	492	(2)
Chiral Poisoning	494	(2)
Enantioselective Activation and Induced Chirality	496	(3)
Chiral Amplification, Chiral Autocatalysis, and the Origin of Natural Chirality	499	(2)
Summary	501	(1)
References	501	(8)
Index	509