Enantioselective Synthesis of Beta–Amino Acids 2e

EUSEBIO JUARISTI is currently Professor of Chemistry at Centro de Investigacion y de Estudios Avanzados del Instituto Politecnico Nacional, Mexico. The author of seven chemistry books, Dr. Juaristi received the Mexican Academy of Sciences Award for Young Scientists in 1988, and the Inter-American Science and Technology Prize of the Organization of American States in 1990. More recently, in 1998, he received the Presidential Medal, the highest recognition for Mexican scientists. VADIM SOLOSHONOK is a professor in the Department of Chemistry and Biochemistry at the University of Oklahoma.

Preface. Preface to the First Edition. Contributors. 1. Structural Types of Relevant b-Amino Acid Targets (Eusebio Juaristi). 1.1 Introduction. 1.2 beta2-Alkyl-beta-Amino Acids. 1.3 beta3-Alkyl-beta-Amino Acids. 1.4 beta2,2-Disubstituted beta-Amino Acids. 1.5 beta2,3-Disubstituted beta-Amino Acids. 1.6 beta3,3-Disubstituted beta-Amino Acids. 1.7 beta2,3,3-Trisubstituted beta-Amino Acids. 1.8 beta2,2,3,3-Tetrasubstituted beta-Amino Acids. 1.9 beta2-Aryl-beta-Amino Acids. 1.10 beta3-Aryl-beta-Amino Acids. 1.11 Olefinic and Alkynyl-beta-Amino Acids. 1.12 alpha,beta-Diamino Acids. 1.13 alpha-Hydroxy-beta-Amino Acids. 1.14 beta-Amino-gamma-Hydroxy Acids. 1.15 Carbocyclic beta-Amino Acids. 1.16 Heterocyclic beta-Amino Acids. References. 2. beta-Amino Acids in Natural Products (Peter Spiteller and Franz von Nussbaum). 2.1 Introduction. 2.2 Natural Products Containing beta-Amino Acids Related to Proteinogenic alpha-Amino Acids. 2.3 Natural Products Containing Unusual Aliphatic beta-Amino Acids. 2.4 Natural Products Containing Aliphatic Hydroxy-beta-Amino Acids. 2.5 Natural Products Containing Aliphatic beta-Amino Acids with Oxo Groups. 2.6 Natural Products Containing Amino-beta-Amino Acids (Except beta-Lysine). 2.7 Alicyclic and Heterocyclic beta-Amino Acids. 2.8 Natural Products Containing Unusual Aromatic beta-Amino Acids. 2.9 Conclusions and Future Prospects. References. 3. Preparation of Enantiopure beta-Amino Acids by Homologation of alpha-Amino Acids (Joachim Podlech). 3.1 Introduction. 3.2 Arndt-Eistert Homologation. 3.3 Homologation of Amino Acids with Concomitant beta-Lactam Formation. 3.4 Homologation of Amino Acids Using Cyano Hydrins. References. 4. Asymmetric Catalysis in Enantioselective Synthesis of beta-Amino Acids (Anna G. Wenzel and Eric N. Jacobsen). 4.1 Introduction. 4.2 Catalytic Asymmetric Conjugate Addition for Preparation of beta-Aliphatic-beta-Amino Acids. 4.3 Asymmetric Mannich Reactions Catalyzed by Thiourea Derivatives for Enantioselective Preparation of beta-Aryl-beta-Amino Acids. References. 5. Enantioselective Synthesis of Conformationally Constrained beta-Amino Acids (Rosa M. Ortuno). 5.1 General Introduction. 5.2 Cycloalkane beta-Amino Acids. 5.3 Alkyl-Substituted beta-Amino Acids. 5.4 Other Methodologies. References. 6. Catalytic Enantioselective Mannich Reactions (Masaharu Ueno and Shu Kobayashi). 6.1 Introduction. 6.2 Catalytic Enantioselective Mannich Reactions Using Chiral Lewis Acid Catalysts. 6.3 Catalytic Asymmetric Mannich Reactions via Metal Enolates. 6.4 Catalytic Asymmetric Reaction Using an Organocatalyst. 6.5 Miscellaneous. References. 7. Enantioselective Synthesis of beta-Amino Acids via Stereoselective Hydrogenation of beta-Aminoacrylic Acid Derivatives (Eusebio Juaristi, V& acute;ctor Manuel Gutierrez-Garc& acute;a, and Heraclio Lopez-Ruiz) 7.1 Introduction. 7.2 Recent Developments: Rhodium Complexes with Chiral Phosphorus Bidentate Ligands. 7.3 Recent Developments: Rhodium Complexes with Chiral Phosphorus Monodentate Ligands. 7.4 Recent Developments: Ruthenium Complexes with Chiral Phosphorus Bidentate Ligands. References. 8. Asymmetric Synthesis of beta-Amino Acids by Enolate Additions to tert-Butanesulfinyl Imines (Kristin Brinner and Jonathan A. Ellman). 8.1 Introduction. 8.2 Synthesis of N-tert-Butanesulfinyl Imines. 8.3 Synthesis of N-Sulfinyl-Protected beta-Amino Acids. 8.4 N-tert-Butanesulfinyl Protecting Group. 8.5 Synthetic Utility. 8.6 Summary. References. 9. Organocatalytic Approaches to Enantioenriched beta-Amino Acids (Fujie Tanaka and Carlos F. Barbas, III). 9.1 Introduction. 9.2 Mannich-Type Reactions Using Aldehydes and alpha-Ethyl Glyoxylate. 9.3 Mannich-Type Reactions Using Aldehydes and Preformed Aldimines. 9.4 Three-Component Mannich Reactions Using Aldehyde Donors. 9.5 Proposed Mechanism for -Proline-Catalyzed Mannich Reactions. 9.6 Transformation of Product of -Proline-Catalyzed Mannich Reaction into beta-Amino Acid and beta-Lactams. 9.7 One-Pot Transformations via -Proline-Catalyzed Mannich Reactions Using Aldehydes as Nucleophiles. 9.8 Mannich Reactions Using alpha,alpha-Disubstituted Aldehydes or alpha-Imidoaldehyde for Preparation of Highly Functionalized beta-Amino Acid Derivatives. 9.9 Other Organocatalytic Reactions for Preparation of Enantioenriched beta-Amino Acids. 9.10 Summary. References. 10. Asymmetric Synthesis of Cyclic &Beat;-Amino Acids via Cycloaddition Reactions (Jose Barluenga, Bernardo Olano, Josefa Florez, and Carlos Valdes). 10.1 Introduction. 10.2 General Strategies in Asymmetric Synthesis of Cyclic beta-Amino Acids. 10.3 Cyclic beta-Amino Acids via Cycloaddition Reactions. 10.4 Synthesis of cis- and trans-2-Aminocyclohexanecarboxylic Acid Derivatives via [4 + 2]-Cycloaddition Reactions. 10.5 Synthesis of beta-Proline Derivatives via [3 + 2]-Cycloaddition Reactions. 10.6 Synthesis of Constrained Six-Membered Ring alpha,alpha-Disubstituted beta-Amino Acid Derivatives via [4 + 2]-Cycloaddition Reactions. 10.7 Summary. References. 11. Enantioselective Synthesis of Novel beta-Amino Acids (Javed Iqbal and Saibal Kumar Das). 11.1 Acyclic Amino Acids. 11.2 Cyclic and Conformationally Constrained beta-Amino Acids. 11.3 Conclusion. References. 12. Asymmetric Synthesis of Phosphonic Analogs of beta-Amino Acids (Marian Miko ajczyk, Jozef Drabowicz, and Piotr Lyzwa). 12.1 Enantioselective C-C Bond-Forming Reactions. 12.2 Enantioselective C-N Bond-Forming Reactions. 12.3 Enantioselective C-H Bond-Forming Reactions. 12.4 Miscellaneous. References. 13. Asymmetric Synthesis of alpha-Substituted-beta-Amino Phosphonates and Phosphinates and beta-Amino Sulfur Analogs (Francisco Palacios, Concepcion Alonso, and Jesus de los Santos). 13.1 Introduction. 13.2 Synthesis of alpha-Alkyl-beta-Amino Phosphorus Derivatives. 13.3 Synthesis of beta-Amino-alpha-Hydroxy Phosphonic and Phosphinic Acid Derivatives. 13.4 Synthesis of beta-Amino-alpha-Halogenated Phosphonates. 13.5 Synthesis of alpha, beta-Diamino Phosphonates and Phosphinates. 13.6 beta-Amino-a-Substituted Phosphorus Derivatives with Peptide Bond Formation: beta-Amino-alpha-Substituted Phosphonoand Phosphinopeptides. 13.7 beta-Amino Sulfur Analogs. 13.8 Conclusion. References. 14. Stereoselective Synthesis of Fluorine-Containing beta-Amino Acids (Santos Fustero, Juan F. Sanz-Cervera, and Vadim A. Soloshonok). 14.1 Introduction. 14.2 Acyclic Fluorinated alpha, beta-Disubstituted beta-Amino Acids. 14.3 Cyclic Fluorinated alpha, beta-Disubstituted beta-Amino Acids. 14.4 a-Fluoroalkyl beta-Amino Acids. 14.5 beta-Fluoroalkyl beta-Amino Acids. 14.6 beta-Substituted alpha, alpha-Difluoro-beta-Amino Acids. References. 15. Enantioselective Synthesis of beta-Amino Acids via Conjugate Addition to alpha, beta-Unsaturated Carbonyl Compounds (Scott J. Miller and David J. Guerin). 15.1 Introduction. 15.2 Diastereoselective Additions to Chiral Michael Acceptors. 15.3 Additions of Chiral Ammonia Equivalents to Michael Acceptors. 15.4 Methods Based on Asymmetric Catalysis. References. 16. Preparation of Enantiopure beta-Amino Acids via Enantioselective Conjugate Addition (Mei Liu and Mukund P. Sibi). 16.1 Introduction. 16.2 Conjugate Addition of Alkyl or Aromatic Amines. 16.3 Addition of Hydroxylamine to Enoates. 16.4 Conjugate Addition of Azide. 16.5 Conjugate Addition of Carbon Nucleophiles. 16.6 Conclusions. References. 17. Biocatalytic Entry to Enantiomerically Pure beta-Amino Acids (Dmitrii O. Berbasov, Trevor K. Ellis, and Vadim A. Soloshonok). 17.1 Introduction. 17.2 Biocatalytic Entry to Enantiomerically Pure beta-Amino Acids. 17.3 Conclusion. References. 18. Stereoselective Synthesis of beta-Amino Acids via Radical Reactions (Takeaki Naito and Okiko Miyata). 18.1 Introduction. 18.2 Synthesis of Acyclic beta-Amino Acids. 18.3 Synthesis of Cyclic beta-Amino Acids. 18.4 Synthesis of beta-Lactams. References. 19. Recent Advances in Synthesis of alpha-Hydroxy-beta-amino Acids and Their Use in SAR Studies of Taxane Anticancer Agents (Jin Chen, Larisa V. Kuznetsova, Ioana M. Ungreanu, and Iwao Ojima). 19.1 Introduction. 19.2 Synthesis of Enantiopure alpha-Hydroxy-beta-amino Acid Components of Taxane Anticancer Agents by beta-Lactam Synthon Method. 19.3 New C-13 alpha-Hydroxy-beta-amino Acid Residues and Their Significance in Second-Generation Taxoids. 19.4 Taxoids with Photoaffinity-Labeled alpha-Hydroxy-beta-amino Acid Residues. 19.5 Taxoids with Fluorine- and Isotope-Labeled alpha-Hydroxy-beta-amino Acid Residues for NMR Studies. 19.6 Summary. References. 20. Synthesis of beta-Amino Acids and Their Derivatives from b-Lactams: Update (Claudio Palomo, Jesus M. Aizpurua, Inaki Ganboa, and Mikel Oiarbide). 20.1 Introduction. 20.2 beta-Lactam Ring Opening by Oxygen Nucleophiles: beta-Amino Esters and Related Products. 20.3 beta-Lactam Ring Opening by Nitrogen Nucleophiles: beta-Amino Amides and b-Amino Acid-Derived Peptides. 20.4 beta-Lactam Ring Opening by Carbon Nucleophiles: beta-Amino Ketones and Related Products. 20.5 Large-Ring Heterocycles from beta-Lactams. 20.6 Concluding Remarks and Prospects. References. 21. Multiple-Component Condensation Methods for Preparation of Combinatorial Libraries of beta-Amino Carbonyl Derivatives (James C. Adrian, Jr.). 21.1 Introduction. 21.2 Mannich Reaction. 21.3 Other Multiple-Component Reactions. 21.4 Solid-Phase MCC Methods. 21.5 Conclusions. References. 22. Using Constrained b-Amino Acid Residues to Control beta-Peptide Shape and Function (Michael A. Gelman and Samuel H. Gellman). 22.1 Introduction: beta-Peptides in the Foldamer Context. 22.2 Monomer Synthesis. 22.3 beta-Peptide Synthesis. 22.4 Conformational Data. 22.5 Biological Applications. 22.6 New Frontiers for beta-Peptide Structure. References. 23. beta2-Amino Acids with Proteinogenic Side Chains and Corresponding Peptides: Synthesis, Secondary Structure, and Biological Activity (Marino A. Campo, Jaime Escalante, and Radovan Scaron;ebesta). 23.1 Introduction. 23.2 Synthesis of beta2-Amino Acids. 23.3 Solution and Solid-Phase Synthesis of Peptides Containing beta2-Amino Acids. 23.4 Secondary Structures of Peptides Containing beta2-Amino Acids. 23.5 Biologically Active Peptides Containing Proteinogenic beta2-Amino Acids. 23.6 Conclusions. Abbreviations. References. Index.