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  Contents  
 
  Foreword V
  Preface XVII
  List of Contributors XIX
1 Stoichiometric Asymmetric Synthesis 1
1.1 Development of Novel Enantioselective Synthetic Methods
Dieter Enders and Wolfgang Bettray 		1
1.1.1 Introduction 1
1.1.2 -Silyl Ketone-Controlled Asymmetric Syntheses 1
1.1.2.1 Regio- and Enantioselective -Fluorination of Ketones 2
1.1.2.2 -Silyl Controlled Asymmetric Mannich Reactions 3
1.1.3 Asymmetric Hetero-Michael Additions 5
1.1.3.1 Asymmetric Aza-Michael Additions 5
1.1.3.2 Asymmetric Oxa-Michael Additions 10
1.1.3.3 Asymmetric Phospha-Michael-Additions 11
1.1.4 Asymmetric Syntheses with Lithiated -Aminonitriles 14
1.1.4.1 Asymmetric Nucleophilic -Aminoacylation 14
1.1.4.2 Asymmetric Nucleophilic Alkenoylation of Aldehydes 16
1.1.5 Asymmetric Electrophilic -Substitution of Lactones and Lactams 18
1.1.6 Asymmetric Synthesis of -Phosphino Ketones and 2-Phosphino Alcohols 22
1.1.7 Asymmetric Synthesis of 1,3-Diols and anti-1,3-Polyols 24
1.1.8 Asymmetric Synthesis of -Substituted Sulfonamides and Sulfonates 26
1.2 Asymmetric Synthesis of Natural Products Employing the SAMP/RAMP Hydrazone Methodology 38
Dieter Enders and Wolfgang Bettray
1.2.1 Introduction 38
1.2.2 Stigmatellin A 38
1.2.3 Callistatin A 41
1.2.4 Dehydroiridodiol(dial) and Neonepetalactone 51
1.2.5 First Enantioselective Synthesis of Dendrobatid Alkaloids Indolizidine 209I and 223J 53
1.2.6 Efficient Synthesis of (2S,12´R)-2-(12´-Aminotridecyl)pyrrolidine, a Defense Alkaloid of the Mexican Bean Beetle 57
1.2.7 2-epi-Deoxoprosopinine 58
1.2.8 Attenol A and B 62
1.2.9 Asymmetric Synthesis of (+)- and (-)-Streptenol A 64
1.2.10 Sordidin 66
1.2.11 Prelactone B and V 69
1.3 Asymmetric Synthesis Based on Sulfonimidoyl-Substituted Allyltitanium Complexes
Hans-Joachim Gais 		75
1.3.1 Introduction 75
1.3.2 Hydroxyalkylation of Sulfonimidoyl-Substituted Allylltitanium Complexes 80
1.3.2.1 Sulfonimidoyl-Substituted Bis(allyl)titanium Complexes 80
1.3.2.2 Sulfonimidoyl-Substituted Mono(allyl)tris(diethylamino)titanium Complexes 82
1.3.3 Aminoalkylation of Sulfonimidoyl-Substituted Allyltitanium Complexes 85
1.3.3.1 Sulfonimidoyl-Substituted Bis(allyl)titanium Complexes 85
1.3.3.2 Sulfonimidoyl-Substituted Mono(allyl)tris(diethylamino)titanium Complexes 86
1.3.4 Structure and Reactivity of Sulfonimidoyl-Substituted Allyltitanium Complexes 88
1.3.4.1 Sulfonimidoyl-Substituted Bis(allyl)titanium Complexes 88
1.3.4.2 Sulfonimidoyl-Substituted Mono(allyl)titanium Complexes 91
1.3.5 Asymmetric Synthesis of Homopropargyl Alcohols 95
1.3.6 Asymmetric Synthesis of 2,3-Dihydrofurans 96
1.3.7 Synthesis of Bicyclic Unsaturated Tetrahydrofurans 98
1.3.8 Asymmetric Synthesis of Alkenyloxiranes 100
1.3.9 Asymmetric Synthesis of Unsaturated Mono- and Bicyclic Prolines 102
1.3.10 Asymmetric Synthesis of Bicyclic Amino Acids 105
1.3.11 Asymmetric Synthesis of -Amino Acids 108
1.3.12 Conclusion 111
1.4 The “Daniphos” Ligands: Synthesis and Catalytic Applications 115
Albrecht Salzer and Wolfgang Braun
1.4.1 Introduction 115
1.4.2 General Synthesis 116
1.4.3 Applications in Stereoselective Catalysis 120
1.4.3.1 Enantioselective Hydrogenations 120
1.4.3.2 Diastereoselective Hydrogenation of Folic Acid Ester 122
1.4.3.3 Enantioselective Isomerization of Geranylamine to Citronellal 124
1.4.3.4 Nucleophilic Asymmetric Ring-Opening of Oxabenzonorbornadiene 124
1.4.3.5 Enantioselective Suzuki Coupling 126
1.4.3.6 Asymmetric Hydrovinylation 126
1.4.3.7 Allylic Sulfonation 128
1.4.4 Conclusion 129
1.5 New Chiral Ligands Based on Substituted Heterometallocenes 130
Christian Ganter
1.5.1 Introduction 130
1.5.2 General Properties of Phosphaferrocenes 131
1.5.3 Synthesis of Phosphaferrocenes 132
1.5.4 Preparation of Bidentate P,P and P,N Ligands 133
1.5.5 Modification of the Backbone Structure 136
1.5.6 Cp–Phosphaferrocene Hybrid Systems 139
1.5.7 Catalytic Applications 145
1.5.8 Conclusion 146
2 Catalytic Asymmetric Synthesis 149
2.1 Chemical Methods 149
2.1.1 Sulfoximines as Ligands in Asymmetric Metal Catalysis
Carsten Bolm 		149
2.1.1.1 Introduction 149
2.1.1.2 Development of Methods for Sulfoximine Modification 150
2.1.1.3 Sulfoximines as Ligands in Asymmetric Metal Catalysis 162
2.1.1.4 Conclusions 170
2.1.2 Catalyzed Asymmetric Aryl Transfer Reactions
Carsten Bolm 		176
2.1.2.1 Introduction 176
2.1.2.2 Catalyst Design 177
2.1.2.3 Catalyzed Aryl Transfer Reactions 180
2.1.3 Substituted [2.2]Paracyclophane Derivatives as Efficient Ligands for Asymmetric 1,2- and 1,4-Addition Reactions 196
Stefan Bräse
2.1.3.1 [2.2]Paracyclophanes as Chiral Ligands 196
2.1.3.2 Synthesis of [2.2]Paracyclophane Ligands 199
2.1.3.2.1 Preparation of FHPC-, AHPC-, and BHPC-Based Imines 199
2.1.3.2 Structural Information on AHPC-Based Imines 199
2.1.3.3 Asymmetric 1,2-Addition Reactions to Aryl Aldehydes 200
2.1.3.3.1 Initial Considerations 200
2.1.3.3.2 Asymmetric Addition Reactions to Aromatic Aldehydes: Scope of Substrates 203
2.1.3.4 Asymmetric Addition Reactions to Aliphatic Aldehydes 205
2.1.3.5 Addition of Alkenylzinc Reagents to Aldehydes 206
2.1.3.6 Asymmetric Conjugate Addition Reactions 208
2.1.3.7 Asymmetric Addition Reactions to Imines 208
2.1.3.8 Asymmetric Addition Reactions on Solid Supports 212
2.1.3.8.1 Applications 213
2.1.3.9 Conclusions and Future Perspective 213
2.1.4 Palladium-Catalyzed Allylic Alkylation of Sulfur and Oxygen Nucleophiles – Asymmetric Synthesis, Kinetic Resolution and Dynamic Kinetic Resolution
Hans-Joachim Gais 		215
2.1.4.1 Introduction 215
2.1.4.2 Asymmetric Synthesis of Allylic Sulfones and Allylic Sulfides and Kinetic Resolution of Allylic Esters 216
2.1.4.2.1 Kinetic Resolution 216
2.1.4.2.2 Selectivity 220
2.1.4.2.3 Asymmetric Synthesis 220
2.1.4.2.4 Synthesis of Enantiopure Allylic Alcohols 224
2.1.4.3 Asymmetric Rearrangment and Kinetic Resolution of Allylic Sulfinates 225
2.1.4.3.1 Introduction 225
2.1.4.3.2 Synthesis of Racemic Allylic Sulfinates 225
2.1.4.3.3 Pd-Catalyzed Rearrangement 226
2.1.4.3.4 Kinetic Resolution 227
2.1.4.3.5 Mechanistic Considerations 228
2.1.4.4 Asymmetric Rearrangment of Allylic Thiocarbamates 229
2.1.4.4.1 Introduction 229
2.1.4.4.2 Synthesis of Racemic O-Allylic Thiocarbamates 229
2.1.4.4.3 Acyclic Carbamates 229
2.1.4.4.4 Cyclic Carbamates 231
2.1.4.4.5 Mechanistic Considerations 232
2.1.4.4.6 Synthesis of Allylic Sulfides 232
2.1.4.5 Asymmetric Synthesis of Allylic Thioesters and Kinetic Resolution of Allylic Esters 233
2.1.4.5.1 Introduction 233
2.1.4.5.2 Asymmetric Synthesis of Allylic Thioesters 234
2.1.4.5.3 Kinetic Resolution of Allylic Esters 235
2.1.4.5.4 Memory Effect and Dynamic Kinetic Resolution of the Five-Membered Cyclic Acetate 238
2.1.4.5.5 Asymmetric Synthesis of Cyclopentenyl Thioacetate 242
2.1.4.6 Kinetic and Dynamic Kinetic Resolution of Allylic Alcohols 242
2.1.4.6.1 Introduction 242
2.1.4.6.2 Asymmetric Synthesis of Symmetrical Allylic Alcohols 242
2.1.4.6.3 Asymmetric Synthesis of Unsymmetrical Allylic Alcohols 244
2.1.4.6.4 Asymmetric Synthesis of a Prostaglandin Building Block 245
2.1.4.6.5 Investigation of an Unsaturated Analogue of BPA 245
2.1.4.7 Conclusions 246
2.1.5 The QUINAPHOS Ligand Family and its Application in Asymmetric Catalysis
Giancarlo Franciò, Felice Faraone, and Walter Leitner 		250
2.1.5.1 Introduction 250
2.1.5.2 Synthetic Strategy 252
2.1.5.3 Stereochemistry and Coordination Properties 254
2.1.5.3.1 Free Ligands 254
2.1.5.3.2 Complexes 256
2.1.5.4 Catalytic Applications 261
2.1.5.4.1 Rhodium-Catalyzed Asymmetric Hydroformylation of Styrene 261
2.1.5.4.2 Rhodium-Catalyzed Asymmetric Hydrogenation of Functionalized Alkenes 263
2.1.5.4.3 Ruthenium-Catalyzed Asymmetric Hydrogenation of Aromatic Ketones 265
2.1.5.4.4 Copper-Catalyzed Enantioselective Conjugate Addition of Diethylzinc to Enones 267
2.1.5.4.5 Nickel-Catalyzed Asymmetric Hydrovinylation 268
2.1.5.4.6 Nickel-Catalyzed Cycloisomerization of 1,6-Dienes 270
2.1.5.5 Conclusions 273
2.1.6 Immobilization of Transition Metal Complexes and Their Application to Enantioselective Catalysis 277
Adrian Crosman, Carmen Schuster, Hans-Hermann Wagner, Melinda Batorfi, Jairo Cubillos, and Wolfgang Hölderich
2.1.6.1 Introduction 277
2.1.6.2 Immobilized Rh Diphosphino Complexes as Catalysts for Asymmetric Hydrogenation 278
2.1.6.2.1 Preparation and Characterization of the Immobilized Rh–Diphosphine Complexes 279
2.1.6.2.2 Enantioselective Hydrogenation over Immobilized Rhodium Diphosphine Complexes 282
2.1.6.3 Heterogeneous Asymmetric Epoxidation of Olefins over Jacobsen’s Catalyst Immobilized in Inorganic Porous Materials 284
2.1.6.3.1 Preparation and Characterization of Immobilized Jacobsen’s Catalysts 285
2.1.6.3.2 Epoxidation of Olefins over Immobilized Jacobsen Catalysts 287
2.1.6.4 Novel Heterogenized Catalysts for Asymmetric Ring-Opening Reactions of Epoxides 291
2.1.6.4.1 Synthesis and Characterization of the Heterogenized Catalysts 291
2.1.6.4.2 Asymmetric Ring Opening of Epoxides over New Heterogenized Catalysts 293
2.1.6.5 Conclusions 295
2.2 Biological Methods 298
2.2.1 Directed Evolution to Increase the Substrate Range of Benzoylformate Decarboxylase from Pseudomonas putida
Marion Wendorff, Thorsten Eggert, Martina Pohl, Carola Dresen, Michael Müller, and Karl-Erich Jaeger 		298
2.2.1.1 Introduction 298
2.2.1.2 Materials and Methods 300
2.2.1.2.1 Reagents 300
2.2.1.2.2 Construction of Strains for Heterologous Expression of BFD and BAL 300
2.2.1.2.3 Polymerase Chain Reactions 301
2.2.1.2.4 Generation of a BFD Variant Library by Random Mutagenesis 302
2.2.1.2.5 High-Throughput Screening for Carboligation Activity with the Substrates Benzaldehyde and Dimethoxyacetaldehyde 303
2.2.1.2.6 Expression and Purification of BFD Variants 303
2.2.1.2.7 Protein Analysis Methods 304
2.2.1.2.8 Enzyme Activity Assays 304
2.2.1.3 Results and Discussion 304
2.2.1.3.1 Overexpression of BFD in Escherichia coli 304
2.2.1.3.2 Random Mutagenesis of BFD Variant L476Q 305
2.2.1.3.3 Development of a High-Throughput Screening Assay for Carboligase Activity 305
2.2.1.3.4 Identification of a BFD Variant with an Optimized Acceptor Aldehyde Spectrum 306
2.2.1.3.5 Biochemical Characterization of the BFD Variants 308
2.2.1.3.6 Decreased Benzoyl Formate Decarboxylation Activity of Variant 55E4 308
2.2.1.3.7 Formation of 2-Hydroxy-3,3-dimethoxypropiophenone and Benzoin 308
2.2.1.3.8 Enantioselectivity of the Carboligation Reaction 310
2.2.1.4 Conclusions 311
2.2.2 C–C-Bonding Microbial Enzymes: Thiamine Diphosphate-Dependent Enzymes and Class I Aldolases
Georg A. Sprenger, Melanie Schürmann, Martin Schürmann, Sandra Johnen, Gerda Sprenger, Hermann Sahm, Tomoyuki Inoue, and Ulrich Schörken 		312
2.2.2.1 Introduction 312
2.2.2.2 Thiamine Diphosphate (ThDP)-Dependent Enzymes 312
2.2.2.2.1 Transketolase (TKT) 313
2.2.2.2.2 1-Deoxy-D-xylulose 5-Phosphate Synthase (DXS) 317
2.2.2.2.3 Phosphonopyruvate Decarboxylase (PPD) from Streptomyces viridochromogenes 318
2.2.2.3 Class I Aldolases 318
2.2.2.3.1 Transaldolase (TAL) 320
2.2.2.3.2 Fructose 6-Phosphate Aldolase (FSA) 321
2.2.2.4 Summary and Outlook 321
2.2.3 Enzymes for Carboligation – 2-Ketoacid Decarboxylases and Hydroxynitrile Lyases
Martina Pohl, Holger Breittaupt, Bettina Frölich, Petra Heim, Hans Iding, Bettina Juchem, Petra Siegert, and Maria-Regina Kula 		327
2.2.3.1 Introduction 327
2.2.3.2 2-Ketoacid Decarboxylases 327
2.2.3.2.1 Comparative Biochemical Characterization of Wild-Type PDC and BFD 328
2.2.3.2.2 Identification of Amino Acid Residues Relevant to Substrate Specificity and Enantioselectivity 330
2.2.3.2.3 Optimization of the Substrate Range of BFD by Site-Directed Mutagenesis 330
2.2.3.2.4 Optimization of Stability and Substrate Range of BFD by Directed Evolution 330
2.2.3.3 Hydroxynitrile Lyases 332
2.2.3.3.1 HNL from Sorghum bicolor 333
2.2.3.3.2 HNL from Linum usitatissimum 337
2.2.4 Preparative Syntheses of Chiral Alcohols using (R)-Specific Alcohol Dehydrogenases from Lactobacillus Strains
Andrea Weckbecker, Michael Müller, and Werner Hummel 		341
2.2.4.1 Introduction 341
2.2.4.2 (R)-Specific Alcohol Dehydrogenase from Lactobacillus kefir 341
2.2.4.3 Comparison of (R)-Specific ADHs from L. kefir and L. brevis 342
2.2.4.4 Preparative Applications of ADHs from L. kefir and L. brevis 345
2.2.4.4.1 Synthesis of (R,R)-Diols 346
2.2.4.4.2 Synthesis of Enantiopure 1-Phenylpropane-1,2-diols 346
2.2.4.4.3 Synthesis of Enantiopure Propargylic Alcohols 346
2.2.4.4.4 Regioselective Reduction of t-Butyl 6-chloro-3,5-dioxohexanoate to the Corresponding Enantiopure (S)-5-Hydroxy Compound 346
2.2.4.5 Coenzyme Regeneration and the Construction and Use of “Designer Cells” 347
2.2.4.6 Discussion 349
2.2.5 Biocatalytic C–C Bond Formation in Asymmetric Synthesis
Wolf-Dieter Fessner 		351
2.2.5.1 Introduction 351
2.2.5.2 Enzyme Mechanisms 352
2.2.5.2.1 Class II Aldolases 352
2.2.5.2.2 Class I Fructose 1,6-Bisphosphate Aldolase 355
2.2.5.2.3 Sialic Acid Synthase 355
2.2.5.2.4 Rhamnose Isomerase 356
2.2.5.3 New Synthetic Strategies 357
2.2.5.3.1 Sugar Phosphonates 357
2.2.5.3.2 Xylulose 5-Phosphate 359
2.2.5.3.3 RhuA Stereoselectivity 359
2.2.5.3.4 Aldolase Screening Assay 361
2.2.5.3.5 Aldose Synthesis 361
2.2.5.3.6 Tandem Chain Extension–Isomerization–Chain Extension 362
2.2.5.3.7 Tandem Bidirectional Chain Extensions 363
2.2.5.3.8 Non-Natural Sialoconjugates 369
2.2.5.4 Summary and Outlook 373
2.2.6 Exploring and Broadening the Biocatalytic Properties of Recombinant Sucrose Synthase 1 for the Synthesis of Sucrose Analogues
Lothar Elling 		376
2.2.6.1 Introduction 376
2.2.6.2 Characteristics of Recombinant Sucrose Synthase 1 (SuSy1) Expressed in Saccharomyces cerevisiae 377
2.2.6.2.1 Expression and Purification of SuSy1 from Yeast 377
2.2.6.2.2 The Substrate Spectrum of SuSy1 from Yeast 378
2.2.6.3 Characteristics of Recombinant Sucrose Synthase 1 (SuSy1) Expressed in Escherichia coli 381
2.2.6.3.1 Expression and Purification of SuSy1 from E. coli 381
2.2.6.3.2 The Substrate Spectrum of SuSy1 from E. coli 382
2.2.6.4 Sucrose Synthase 1 Mutants Expressed in S. cerevisiae and E. coli 383
2.2.6.5 Outlook 384
2.2.7 Flexible Asymmetric Redox Reactions and C–C Bond Formation by Bioorganic Synthetic Strategies
Michael Müller, Michael Wolberg, Silke Bode, Ralf Feldmann, Petra Geilenkirchen, Thomas Schubert, Lydia Walter, Werner Hummel, Thomas Dünnwald, Ayhan S. Demir, Doris Kolter-Jung, Adam Nitsche, Pascal Dünkelmann, Annabel Cosp, Martina Pohl, Bettina Lingen, and Maria-Regina Kula 		386
2.2.7.1 Introduction 386
2.2.7.2 Diversity-Oriented Access to 1,3-Diols Through Regio- and Enantioselective Reduction of 3,5-Dioxocarboxylates 386
2.2.7.2.1 Regio- and Enantioselective Enzymatic Reduction 387
2.2.7.2.2 Dynamic Kinetic Resolution 388
2.2.7.2.3 Stereoselective Access to 1,3-Diols by Diastereoselective Reduction 389
2.2.7.2.4 Nucleophilic Substitution of Chlorine 390
2.2.7.2.5 Application in Natural Product Syntheses 391
2.2.7.2.6 Discussion and Outlook 392
2.2.7.3 Chemo- and Enantioselective Reduction of Propargylic Ketones 395
2.2.7.3.1 Enantioselective Reduction of Aryl Alkynones 395
2.2.7.3.2 Synthesis of Enantiopure 3-Butyn-2-ol 396
2.2.7.3.3 Enzymatic Reduction of -Halogenated Propargylic Ketones 397
2.2.7.3.4 Modification of -Halogenated Propargylic Alcohols 398
2.2.7.3.5 Olefinic Substrates 399
2.2.7.3.6 Discussion and Outlook 401
2.2.7.4 Thiamine Diphosphate-Dependent Enzymes: Multi-purpose Catalysts in Asymmetric Synthesis 401
2.2.7.4.1 Formation of Chiral 2-Hydroxy Ketones Through BFD-Catalyzed Reactions 402
2.2.7.4.2 BAL as a Versatile Catalyst for C–C Bond Formation and Cleavage Reactions 405
2.2.7.4.3 Asymmetric Cross-Benzoin Condensation 407
2.2.7.4.4 Discussion and Outlook 408
2.2.7.5 Summary 409
3 Reaction Technology in Asymmetric Synthesis 415
3.1 Reaction Engineering in Asymmetric Synthesis
Stephan Lütz, Udo Kragl, Andreas Liese, and Christian Wandrey 		415
3.1.1 Introduction 415
3.1.2 Membrane Reactors with Chemical Catalysts 418
3.1.3 Membrane Reactors with Biological Catalysts 420
3.1.3.1 Membrane Reactors with Whole Cells 420
3.1.3.2 Membrane Reactors with Isolated Enzymes 421
3.1.4 Two-Phase Systems 422
3.1.5 Conclusions 425
3.2 Biocatalyzed Asymmetric Syntheses Using Gel-Stabilized Aqueous–Organic Two-Phase Systems
Marion B. Ansorge-Schumacher 		427
3.2.1 Gel-Stabilized Two-Phase Systems 428
3.2.2 Benzoin Condensation with Entrapped Benzaldehyde Lyase 430
3.2.3 Reduction of Ketones with Entrapped Alcohol Dehydrogenase 432
3.2.4 Conclusion 433
  Index 435
  Name Index 443

 
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