Modern Aldol Reactions

Modern Aldol Reactions......Page 4
ISBN 3-527-30714-1......Page 5
Foreword......Page 6
Contents of Volume 1......Page 8
Contents of Volume 2......Page 13
Preface......Page 18
List of Contributors......Page 20
1.1 Introduction......Page 22
1.2 The Acid or Base-mediated ‘‘Traditional’’ Aldol Reaction......Page 23
1.3 The Aldol Addition of Preformed Enolates – Stereoselectivity and\rTransition-state Models......Page 30
1.4 Stereoselective Aldol Addition of Lithium, Magnesium and\rSodium Enolates......Page 46
1.5 Conclusion......Page 73
References......Page 74
2.1 Introduction......Page 84
2.2 Additions of Enolates to Ketones......Page 86
2.3 Addition of Enolates Without a-Substituents to Aldehydes......Page 87
2.4 Addition of Enolates with a-Substituents to Aldehydes......Page 93
2.5 Natural Product Synthesis via Titanium Enolate Aldol\rReactions......Page 126
2.6 Typical Experimental Procedures for Generation of Titanium\rEnolates......Page 141
2.7 Conclusion......Page 142
References......Page 143
3.2 Crossed Aldol Reactions Using Boron Enolates......Page 148
3.3 Crossed Aldol Reactions Using Silicon Enolates......Page 158
References......Page 176
4.1 Introduction......Page 182
4.2 Aminocatalysis of the Aldol Reaction......Page 183
4.3 Asymmetric Aminocatalysis of the Aldol Reaction......Page 194
References......Page 217
5.1 Introduction......Page 222
5.2 General Aspects......Page 223
5.3 Pyruvate Aldolases......Page 229
5.4 Dihydroxyacetone Phosphate Aldolases......Page 242
5.5 Transketolase and Related Enzymes......Page 268
5.6 2-Deoxy-D-ribose 5-Phosphate Aldolase......Page 271
5.7 Glycine Aldolases......Page 275
5.8 Recent Developments......Page 278
5.9 Summary and Conclusion......Page 279
Examples of Experimental Procedures......Page 280
References......Page 281
6.2 Generation of Aldolase Antibodies......Page 294
6.3 Aldolase Antibody-catalyzed Aldol and Retro-aldol\rReactions......Page 300
6.4 Aldolase Antibodies for Reactions Related to an Enamine\rMechanism and the Nucleophilic Lysine e-Amino Group......Page 314
6.5 Concise Catalytic Assays for Aldolase Antibody-catalyzed\rReactions......Page 318
6.6 Structures of Aldolase Antibodies and Reaction Mechanism of\rNucleophilic Lysine e-Amino Group......Page 319
6.7 Evolution of Aldolase Antibodies In Vitro......Page 323
6.9 Summary and Conclusion......Page 326
6.10 Experimental Procedures......Page 327
References......Page 328
7.2 History of Epothilones: The Total Synthesis Race......Page 332
7.3 Model Study via Chelation Control in the Aldol Reaction by\rKalesse......Page 340
7.4 Long-range Structural Effects on the Stereochemistry of Aldol\rReactions......Page 343
References......Page 347
1.2 Mukaiyama Aldol Reaction and Related Reactions......Page 350
1.3 Asymmetric Aldol Reactions of a-Isocyanocarboxylates......Page 357
1.4 Summary and Conclusions......Page 364
1.5 Experimental Procedures......Page 367
References......Page 370
2.1 Achiral Boron Lewis Acids......Page 374
2.2 Chiral Boron Lewis Acids......Page 382
2.3 Silicon Lewis Acids......Page 402
Representative Experimental Procedures......Page 412
References......Page 414
3.2 Early Examples......Page 418
3.3 Mukaiyama Aldol Reactions with Cu(II) Complexes......Page 419
3.4 Additions Involving In-Situ Enolate Formation......Page 439
3.5 Conclusions......Page 450
References......Page 451
4.2 Tin-promoted Intermolecular Aldol Reactions......Page 454
4.3 Tin-promoted Intramolecular Aldol Reactions......Page 470
4.4 Chiral Diamine–Sn(II) Complex-promoted Aldol Reactions......Page 473
4.5 Asymmetric Total Syntheses of Complex Molecules Using Chiral\rDiamine–Sn(II) Catalysts......Page 489
4.6 Conclusions......Page 506
4.7 Experimental......Page 507
References......Page 508
5.1 Introduction......Page 516
5.2 The Asymmetric Mukaiyama Aldol Reaction......Page 518
5.3 Asymmetric Hetero Diels–Alder Reaction......Page 524
5.4 Reaction Mechanism......Page 529
5.5 Structure of the Chiral Zirconium Catalyst......Page 533
5.6 Air-stable and Storable Chiral Zirconium Catalyst......Page 536
5.7 Conclusion......Page 539
5.8 Experimental......Page 540
References......Page 541
6.1 Introduction......Page 546
6.2 Direct Aldol Reactions with Methyl Ketones......Page 547
6.3 Direct Aldol Reactions with Methylene Ketones......Page 557
6.4 Direct Aldol Reaction with a-Hydroxyketones......Page 559
6.5 Direct Aldol Reaction with Glycine Schiff Bases......Page 568
6.6 Other Examples......Page 570
6.7 Conclusion......Page 573
6.8 Experimental Section......Page 574
References and Notes......Page 575
7.1 Introduction......Page 578
7.2 Preparation of Enoxytrichlorosilanes......Page 585
7.3 Preparation of Chiral Lewis Bases......Page 598
7.4 Enantioselective Aldol Addition of Achiral\rEnoxytrichlorosilanes......Page 602
7.5 Diastereoselective Additions of Chiral Enoxytrichlorosilanes......Page 621
7.6 Aldol Additions of Aldehyde-derived Enoxytrichlorosilanes......Page 637
7.7 Aldol Addition of Trichlorosilyl Ketene Acetal to Aldehydes and\rKetones......Page 643
7.8 Lewis Base Activation of Lewis Acids – Aldol Additions of Silyl\rEnol Ethers to Aldehydes......Page 647
7.9 Toward a Unified Mechanistic Scheme......Page 654
7.10 Conclusions and Outlook......Page 664
7.11 Representative Procedures......Page 665
References......Page 668
8.2 The Aldol–Tishchenko Reaction......Page 676
8.3 Representative Procedures......Page 690
References......Page 691
Common Abbreviations Used in the Text......Page 692
Index......Page 694