Principles and Applications of Asymmetric Synthesis

525 Pages·2001·22.66 MB·english

by  G. Lin

PrinciplesandApplicationsofAsymmetricSynthesis
Guo-QiangLin,Yue-MingLi,AlbertS.C.Chan
Copyright(2001JohnWiley&Sons,Inc.
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
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CONTENTS
Preface xiii
Abbreviations xv
1 Introduction 1
1.1 The Significance 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 Specific Rotation 17
1.3.2 The Nuclear Magnetic ResonanceMethod 19
1.3.3 Some Other ReagentsforNuclear Magnetic
Resonance Analysis 23
1.3.4 Determining the Enantiomer Composition of Chiral
Glycols or Cyclic Ketones 24
1.3.5 ChromatographicMethodsUsing ChiralColumns 25
1.3.6 CapillaryElectrophoresiswithEnantioselective
Supporting Electrolytes 28
1.4 Determining Absolute Configuration 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
1.4.6 Nuclear Magnetic Resonance Methodfor Relative
ConfigurationDetermination 40
1.5 General StrategiesforAsymmetric Synthesis 47
1.5.1 ‘‘Chiron’’ Approaches 48
1.5.2 AcyclicDiastereoselectiveApproaches 49
1.5.3 Double Asymmetric Synthesis 53
1.6 Examplesof SomeComplicated Compounds 56
1.7 Some CommonDefinitions in AsymmetricSynthesis and
Stereochemistry 62
1.8 References 65
vii
viii CONTENTS
2 a-Alkylation andCatalytic Alkylation ofCarbonylCompounds 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-annularChirality Transfer 79
2.3 Preparation of QuaternaryCarbonCenters 98
2.4 Preparation of a-Amino Acids 103
2.5 Nucleophilic Substitution of ChiralAcetal 103
2.6 ChiralCatalyst-Induced Aldehyde Alkylation: Asymmetric
Nucleophilic Addition 107
2.7 Catalytic Asymmetric Additions of Dialkylzinc to Ketones:
EnantioselectiveFormation of Tertiary Alcohols 118
2.8 Asymmetric Cyanohydrination 118
2.9 Asymmetric a-Hydroxyphosphonylation 124
2.10 Summary 127
2.11 References 127
3 Aldoland Related Reactions 135
3.1 Introduction 135
3.2 Substrate-Controlled Aldol Reaction 138
3.2.1 Oxazolidones as ChiralAuxiliaries: ChiralAuxiliary-
Mediated Aldol-Type Reactions 138
3.2.2 Pyrrolidinesas ChiralAuxiliaries 142
3.2.3 Aminoalcohols as the Chiral Auxiliaries 145
3.2.4 Acylsultam Systems as theChiral Auxiliaries 148
3.2.5 a-Silyl Ketones 150
3.3 Reagent-Controlled Aldol Reactions 150
3.3.1 Aldol CondensationsInduced by Chiral Boron
Compounds 150
3.3.2 Aldol Reactions Controlled by Corey’s Reagents 151
3.3.3 Aldol CondensationsControlled by Miscellaneous
Reagents 154
3.4 ChiralCatalyst-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
3.4.3 Asymmetric Aldol Reactions Catalyzed by Chiral
Lewis Acids 160
3.4.4 CatalyticAsymmetric Aldol Reaction Promoted by
Bimetallic Catalysts:Shibasaki’s System 163
3.5 Double AsymmetricAldolReactions 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
4.1 Asymmetric Epoxidation of Allylic Alcohols: Sharpless
Epoxidation 195
4.1.1 The Characteristics of Sharpless Epoxidation 197
4.1.2 Mechanism 199
4.1.3 Modifications and Improvements of Sharpless
Epoxidation 200
4.2 SelectiveOpening of 2,3-Epoxy Alcohols 204
4.2.1 External Nucleophilic Opening of 2,3-EpoxyAlcohols 205
4.2.2 Opening by IntramolecularNucleophiles 207
4.2.3 Opening by Metallic Hydride Reagents 209
4.2.4 Opening by OrganometallicCompounds 210
4.2.5 Payne Rearrangementand Ring-Opening Processes 211
4.2.6 AsymmetricDesymmetrization of meso-Epoxides 214
4.3 Asymmetric Epoxidation of SymmetricDivinyl Carbinols 217
4.4 Enantioselective Dihydroxylation of Olefins 221
4.5 Asymmetric Aminohydroxylation 232
4.6 Epoxidation of Unfunctionalized Olefins 237
4.6.1 Catalytic Enantioselective Epoxidation of Simple
Olefinsby Salen Complexes 237
4.6.2 Catalytic Enantioselective Epoxidation of Simple
Olefinsby Porphyrin Complexes 243
4.6.3 Chiral Ketone–Catalyzed Asymmetric Oxidation of
Unfunctionalized Olefins 244
4.7 CatalyticAsymmetric Epoxidation of Aldehydes 249
4.8 Asymmetric Oxidation of Enolates for the Preparation of
Optically Active a-Hydroxyl CarbonylCompounds 250
4.8.1 Substrate-Controlled Reactions 251
4.8.2 Reagent-ControlledReactions 252
4.9 Asymmetric Aziridinationand Related Reactions 255
4.9.1 AsymmetricAziridination 255
4.9.2 RegioselectiveRing Opening of Aziridines 257
4.10 Summary 260
4.11 References 261
x CONTENTS
5 Asymmetric Diels-Alder and Other Cyclization Reactions 267
5.1 ChiralDienophiles 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 Sulfinyl-Substituted Compounds as
Dienophiles 277
5.2 ChiralDienes 277
5.3 Double AsymmetricCycloaddition 278
5.4 ChiralLewis 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 AcyloxyBoraneCatalysts 283
5.4.5 BrønstedAcid–Assisted ChiralLewisAcidCatalysts 285
5.4.6 Bis(Oxazoline) Catalysts 287
5.4.7 Amino AcidSalts asLewis Acids forAsymmetric
Diels-AlderReactions 289
5.5 Hetero Diels-Alder Reactions 290
5.5.1 Oxo Diels-AlderReactions 290
5.5.2 Aza Diels-Alder Reactions 296
5.6 Formation of Quaternary Stereocenters Through Diels-Alder
Reactions 301
5.7 Intramolecular Diels-Alder Reactions 301
5.8 RetroDiels-Alder Reactions 306
5.9 Asymmetric Dipolar Cycloaddition 308
5.10 Asymmetric Cyclopropanation 313
5.10.1 TransitionMetal Complex–Catalyzed
Cyclopropanations 314
5.10.2 The Catalytic Asymmetric Simmons-Smith Reaction 319
5.11 Summary 322
5.12 References 323
6 Asymmetric CatalyticHydrogenation and Other Reduction
Reactions 331
6.1 Introduction 331
6.1.1 Chiral Phosphine Ligandsfor Homogeneous
Asymmetric CatalyticHydrogenation 332
6.1.2 Asymmetric CatalyticHydrogenation of CbC Bonds 334
6.2 Asymmetric Reduction ofCarbonyl Compounds 355
6.2.1 Reductionby BINAL–H 356
CONTENTS xi
6.2.2 Transition Metal–Complex Catalyzed Hydrogenation
of Carbonyl Compounds 359
6.2.3 The OxazaborolidineCatalyst System 367
6.3 Asymmetric Reductionof Imines 373
6.4 Asymmetric Transfer Hydrogenation 377
6.5 Asymmetric Hydroformylation 384
6.6 Summary 388
6.7 References 389
7 Applications of Asymmetric Reactions in the Synthesis ofNatural
Products 397
7.1 The Synthesis of Erythronolide A 397
7.2 The Synthesis of 6-Deoxyerythronolide 400
7.3 The Synthesis of RifamycinS 403
7.3.1 Kishi’s Synthesisin 1980 404
7.3.2 Kishi’s Synthesisin 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 Synthesisof the o-SideChain 415
7.4.3 The Enantioselective Synthesis of (R)-4-Hydroxy-2-
Cyclopentenone 417
7.5 The TotalSynthesis of Taxol—AChallenge and
Opportunity for Chemists Working inthe Area of
Asymmetric Synthesis 418
7.5.1 Synthesisof BaccatinIII,thePolycyclicPart of Taxol 419
7.5.2 AsymmetricSynthesis of the Taxol Side Chain 442
7.6 Summary 445
7.7 References 446
8 Enzymatic Reactions andMiscellaneous 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 Biocatalystsfrom Cultured PlantCells 458
8.2 Miscellaneous Methods 458
8.2.1 AsymmetricSynthesis Catalyzed by Chiral
Ferrocenylphosphine Complex 458
8.2.2 AsymmetricHydrosilylationof Olefins 459
8.2.3 Synthesisof ChiralBiaryls 460
xii CONTENTS
8.2.4 The Asymmetric Kharasch Reaction 464
8.2.5 Optically Active LactonesfromMetal-Catalyzed
Baeyer-Villiger–Type Oxidations Using Molecular
OxygenastheOxidant 465
8.2.6 Recent Progressin Asymmetric Wittig-Type
Reactions 466
8.2.7 Asymmetric Reformatsky Reactions 469
8.2.8 CatalyticAsymmetric Wacker Cyclization 470
8.2.9 Palladium-Catalyzed Asymmetric Alkenylation of
Cyclic Olefins 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 Synthesisof Fluorinated Compounds 481
8.3 New Concepts inAsymmetricReaction 484
8.3.1 Ti CatalystsfromSelf-Assembly Components 484
8.3.2 Desymmetrization 486
8.3.3 Cooperative Asymmetric Catalysis 486
8.3.4 Stereochemical Nonlinear E¤ects inAsymmetric
Reaction 492
8.3.5 Chiral Poisoning 494
8.3.6 Enantioselective Activationand Induced Chirality 496
8.4 ChiralAmplification, Chiral Autocatalysis, and theOrigin of
Natural Chirality 499
8.5 Summary 501
8.6 References 501
Index 509