Enantioselective Synthesis of Beta-Amino Acids

by Juaristi, Eusebio; Soloshonok, Vadim A.

• ISBN13: 9780471467380
• ISBN10: 0471467383
• Edition: 2nd
• Format: Hardcover
• Copyright: 2005-04-21
• Publisher: Wiley-VCH

Summary

Covers all facets of the synthesis of ß-amino acids As evidenced by an exponential increase in the literature published on the subject, interest in ß-amino acids has grown over the past several years. With major pharmaceutical applications, these amino acids are now studied across multiple lines of research, including combinatorial chemistry, medicinal chemistry, molecular design, proteomics, and others. This Second Edition of Enantioselective Synthesis of ß-Amino Acids updates reviews included in the First Edition while also covering new developments since its publication. The book presents detailed discussions of the most important methods for the synthesis of ß-amino acids. In most cases, the lead chemist who originally developed a method provides an authoritative description of it. In addition, Enantioselective Synthesis of ß-Amino Acids, Second Edition: * Features introductory overviews on the structural types of relevant ß-amino acid targets and salient ß-amino acids present in natural products * Dedicates several chapters to advances in the synthesis of oligomers from ß-amino acids * Includes general and practical procedures for the preparation of ß-amino acids in each chapter * Discusses the most important methods that have been recently developed for the asymmetric synthesis of cyclic and open-chain ß-amino acids * Includes a report on the preparation of libraries of enantiopure ß-amino acids using combinatorial approaches The only book of its kind available today, Enantioselective Synthesis of ß-Amino Acids, Second Edition offers upper-level students and professionals an essential resource for pharmaceutical development, medicinal chemistry, and biochemistry.

Author Biography

EUSEBIO JUARISTI is currently Professor of Chemistry at Centro de Investigación y de Estudios Avanzados del Instituto Politécnico 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.

Table of Contents

Preface	xiii
Preface to the First Edition	xv
Contributors	xvii
1. Structural Types of Relevant β-Amino Acid Targets	1	(18)
Eusebio Juaristi
1.1 Introduction	1	(2)
1.2 β²-Alkyl-β-Amino Acids	3	(1)
1.3 β³-Alkyl-β-Amino Acids	3	(1)
1.4 β²,²-Disubstituted β-Amino Acids	4	(1)
1.5 β²,³-Disubstituted β-Amino Acids	4	(1)
1.6 β²,³-Disubstituted β-Amino Acids	5	(1)
1.7 β²,²,³-Trisubstituted β-Amino Acids	6	(1)
1.8 β²,²,³,³-Tetrasubstituted β-Amino Acids	7	(1)
1.9 β²-Aryl-β-Amino Acids	7	(1)
1.10 β³-Aryl-β-Amino Acids	7	(2)
1.11 Olefinic and Alkynyl-β-Amino Acids	9	(2)
1.12 α,β-Diamino Acids	11	(1)
1.13 α-Hydroxy-β-Amino Acids	12	(1)
1.14 β-Amino-γ-Hydroxy Acids	12	(1)
1.15 Carbocyclic β-Amino Acids	13	(1)
1.16 Heterocyclic β-Amino Acids	13	(1)
References	14	(5)
2. β-Amino Acids in Natural Products	19	(74)
Peter Spiteller and Franz von Nussbaum
2.1 Introduction	19	(4)
2.2 Natural Products Containing β-Amino Acids Related to Proteinogenic α-Amino Acids	23	(14)
2.3 Natural Products Containing Unusual Aliphatic β-Amino Acids	37	(10)
2.4 Natural Products Containing Aliphatic Hydroxy-β-Amino Acids	47	(4)
2.5 Natural Products Containing Aliphatic β-Amino Acids with Oxo Groups	51	(2)
2.6 Natural Products Containing Amino-β-Amino Acids (Except β-Lysine)	53	(8)
2.7 Alicyclic and Heterocyclic β-Amino Acids	61	(3)
2.8 Natural Products Containing Unusual Aromatic β-Amino Acids	64	(9)
2.9 Conclusions and Future Prospects	73	(2)
References	75	(18)
3. Preparation of Enantiopure β-Amino Acids by Homologation of α-Amino Acids	93	(14)
Joachim Podlech
3.1 Introduction	93	(1)
3.2 Arndt-Eistert Homologation	93	(7)
3.3 Homologation of Amino Acids with Concomitant β-Lactam Formation	100	(3)
3.4 Homologation of Amino Acids Using Cyano Hydrins	103	(1)
References	104	(3)
4. Asymmetric Catalysis in Enantioselective Synthesis of β-Amino Acids	107	(10)
Anna G. Wenzel and Eric N. Jacobsen
4.1 Introduction	107	(1)
4.2 Catalytic Asymmetric Conjugate Addition for Preparation of β-Aliphatic-β-Amino Acids	107	(3)
4.3 Asymmetric Mannich Reactions Catalyzed by Thiourea Derivatives for Enantioselective Preparation of β-Aryl-β-Amino Acids	110	(4)
References	114	(3)
5. Enantioselective Synthesis of Conformationally Constrained β-Amino Acids	117	(22)
Rosa M. Ortuño
5.1 General Introduction	117	(1)
5.2 Cycloalkane β-Amino Acids	117	(10)
5.3 Alkyl-Substituted β-Amino Acids	127	(7)
5.4 Other Methodologies	134	(3)
References	137	(2)
6. Catalytic Enantioselective Mannich Reactions	139	(20)
Masaharu Ueno and Shu Kobayashi
6.1 Introduction	139	(1)
6.2 Catalytic Enantioselective Mannich Reactions Using Chiral Lewis Acid Catalysts	140	(10)
6.3 Catalytic Asymmetric Mannich Reactions via Metal Enolates	150	(1)
6.4 Catalytic Asymmetric Reaction Using an Organocatalyst	151	(3)
6.5 Miscellaneous	154	(1)
References	154	(5)
7. Enantioselective Synthesis of β-Amino Acids via Stereoselective Hydrogenation of β-Aminoacrylic Acid Derivatives	159	(22)
Eusebio Juaristi, Victor Manuel Gutiérrez-Garcia, and Heraclio López-Ruiz
7.1 Introduction	159	(3)
7.2 Recent Developments: Rhodium Complexes with Chiral Phosphorus Bidentate Ligands	162	(11)
7.3 Recent Developments: Rhodium Complexes with Chiral Phosphorus Monodentate Ligands	173	(1)
7.4 Recent Developments: Ruthenium Complexes with Chiral Phosphorus Bidentate Ligands	174	(4)
References	178	(3)
8. Asymmetric Synthesis of β-Amino Acids by Enolate Additions to tert-Butanesulfinyl Imines	181	(14)
Kristin Brinner and Jonathan A. Ellman
8.1 Introduction	181	(1)
8.2 Synthesis of N-tert-Butanesulfinyl 1mines	181	(2)
8.3 Synthesis of N-Sulfinyl-Protected β-Amino Acids	183	(2)
8.4 N-tert-Butanesulfinyl Protecting Group	185	(1)
8.5 Synthetic Utility	186	(6)
8.6 Summary	192	(1)
References	193	(2)
9. Organocatalytic Approaches to Enantioenriched β-Amino Acids	195	(20)
Fujie Tanaka and Carlos F. Bathos, III
9.1 Introduction	195	(3)
9.2 Mannich-Type Reactions Using Aldehydes and α-Ethyl Glyoxylate	198	(1)
9.3 Mannich-Type Reactions Using Aldehydes and Preformed Aldimines	199	(3)
9.4 Three-Component Mannich Reactions Using Aldehyde Donors	202	(2)
9.5 Proposed Mechanism for L-Proline-Catalyzed Mannich Reactions	204	(1)
9.6 Transformation of Product of L-Proline-Catalyzed Mannich Reaction into β-Amino Acid and β-Lactams	204	(1)
9.7 One-Pot Transformations via L-Proline-Catalyzed Mannich Reactions Using Aldehydes as Nucleophiles	205	(1)
9.8 Mannich Reactions Using α,α-Disubstituted Aldehydes or α-Imidoaldehyde for Preparation of Highly Functionalized β-Amino Acid Derivatives	206	(2)
9.9 Other Organocatalytic Reactions for Preparation of Enantioenriched β-Amino Acids	208	(3)
9.10 Summary	211	(1)
References	212	(3)
10. Asymmetric Synthesis of Cyclic β-Amino Acids via Cycloaddition Reactions	215	(26)
José Barluenga, Bernardo Olano, Josefa Flórez, and Carlos Valdés
10.1 Introduction	215	(1)
10.2 General Strategies in Asymmetric Synthesis of Cyclic β-Amino Acids	216	(2)
10.3 Cyclic β-Amino Acids via Cycloaddition Reactions	218	(4)
10.4 Synthesis of cis- and trans-2-Aminocyclohexanecarboxylic Acid Derivatives via [4 + 2]-Cycloaddition Reactions	222	(5)
10.5 Synthesis of β-Proline Derivatives via [3 + 2]-Cycloaddition Reactions	227	(7)
10.6 Synthesis of Constrained Six-Membered Ring α,α-Disubstituted β-Amino Acid Derivatives via [4 + 2]-Cycloaddition Reactions	234	(2)
10.7 Summary	236	(1)
References	237	(4)
11. Enantioselective Synthesis of Novel β-Amino Acids	241	(20)
Javed Iqbal and Saibal Kumar Das
11.1 Acyclic Amino Acids	242	(12)
11.2 Cyclic and Conformationally Constrained β-Amino Acids	254	(3)
11.3 Conclusion	257	(2)
References	259	(2)
12. Asymmetric Synthesis of Phosphonic Analogs of β-Amino Acids	261	(16)
Marian Mikolajczyk, Józef Drabowicz, and Piotr Lyzwa
12.1 Enantioselective C-C Bond-Forming Reactions	262	(5)
12.2 Enantioselective C-N Bond-Forming Reactions	267	(7)
12.3 Enantioselective C-H Bond-Forming Reactions	274	(1)
12.4 Miscellaneous	275	(1)
References	276	(1)
13. Asymmetric Synthesis of α-Substituted-β-Amino Phosphonates and Phosphinates and β-Amino Sulfur Analogs	277	(42)
Francisco Palacios, Concepción Alonso, and Jesús de los Santos
13.1 Introduction	277	(1)
13.2 Synthesis of α-Alkyl-β-Amino Phosphorus Derivatives	278	(1)
13.3 Synthesis of β-Amino-α-Hydroxy Phosphonic and Phosphinic Acid Derivatives	279	(12)
13.4 Synthesis of β-Amino-α-Halogenated Phosphonates	291	(1)
13.5 Synthesis of α,β-Diamino Phosphonates and Phosphinates	292	(2)
13.6 β-Amino-α-Substituted Phosphorus Derivatives with Peptide Bond Formation: β-Amino-α-Substituted Phosphono- and Phosphinopeptides	294	(7)
13.7 β-Amino Sulfur Analogs	301	(12)
13.8 Conclusion	313	(1)
References	314	(5)
14. Stereoselective Synthesis of Fluorine-Containing β-Amino Acids	319	(32)
Santos Fustero, Juan F. Sanz-Cervera, and iVadim A. Soloshonok
14.1 Introduction	319	(1)
14.2 Acyclic Fluorinated α,β-Disubstituted β-Amino Acids	320	(18)
14.3 Cyclic Fluorinated α,β-Disubstituted β-Amino Acids	338	(2)
14.4 α-Fluoroalkyl β-Amino Acids	340	(3)
14.5 β-Fluoroalkyl β-Amino Acids	343	(3)
14.6 β-Substituted α,α-Difluoro-β-Amino Acids	346	(3)
References	349	(2)
15. Enantioselective Synthesis of β-Amino Acids via Conjugate Addition to α,β-Unsaturated Carbonyl Compounds	351	(26)
Scott J. Miller and David J. Guerin
15.1 Introduction	351	(1)
15.2 Diastereoselective Additions to Chiral Michael Acceptors	352	(4)
15.3 Additions of Chiral Ammonia Equivalents to Michael Acceptors	356	(8)
15.4 Methods Based on Asymmetric Catalysis	364	(10)
References	374	(3)
16. Preparation of Enantiopure β-Amino Acids via Enantioselective Conjugate Addition	377	(20)
Mei Liu and Mukund P. Sibi
16.1 Introduction	377	(1)
16.2 Conjugate Addition of Alkyl or Aromatic Amines	378	(4)
16.3 Addition of Hydroxylamine to Enoates	382	(7)
16.4 Conjugate Addition of Azide	389	(1)
16.5 Conjugate Addition of Carbon Nucleophiles	390	(3)
16.6 Conclusions	393	(1)
References	394	(3)
17. Biocatalytic Entry to Enantiomerically Pure β-Amino Acids	397	(18)
Dmitrii O. Berbasov, Trevor K. Ellis, and Vadim A. Soloshonok
17.1 Introduction	397	(1)
17.2 Biocatalytic Entry to Enantiomerically Pure β-Amino Acids	398	(15)
17.3 Conclusion	413	(1)
References	414	(1)
18. Stereoselective Synthesis of β-Amino Acids via Radical Reactions	415	(32)
Takeaki Naito and Okiko Miyata
18.1 Introduction	415	(2)
18.2 Synthesis of Acyclic β-Amino Acids	417	(15)
18.3 Synthesis of Cyclic β-Amino Acids	432	(4)
18.4 Synthesis of β-Lactams	436	(9)
References	445	(2)
19. Recent Advances in Synthesis of α-Hydroxy-β-amino Acids and Their Use in SAR Studies of Taxane Anticancer Agents	447	(30)
Jin Chen, Larisa V. Kuznetsova, Maria M. Ungreanu, and Iwao Ojima
19.1 Introduction	447	(2)
19.2 Synthesis of Enantiopure α-Hydroxy-β-amino Acid Components of Taxane Anticancer Agents by β-Lactam Synthon Method	449	(5)
19.3 New C-13 α-Hydroxy-β-amino Acid Residues and Their Significance in Second-Generation Taxoids	454	(11)
19.4 Taxoids with Photoaffinity-Labeled α-Hydroxy-β-amino Acid Residues	465	(4)
19.5 Taxoids with Fluorine- and Isotope-Labeled α-Hydroxy-β-amino Acid Residues for NMR Studies	469	(1)
19.6 Summary	470	(1)
References	471	(6)
20. Synthesis of β-Amino Acids and Their Derivatives from β-Lactams: Update	477	(20)
Claudio Palomo, Jesús M. Aizpurua, Iñaki Ganboa, and Mikel Oiarbide
20.1 Introduction	477	(1)
20.2 β-Lactam Ring Opening by Oxygen Nucleophiles: β-Amino Esters and Related Products	478	(6)
20.3 β-Lactam Ring Opening by Nitrogen Nucleophiles: β-Amino Amides and β-Amino Acid-Derived Peptides	484	(5)
20.4 β-Lactam Ring Opening by Carbon Nucleophiles: β-Amino Ketones and Related Products	489	(2)
20.5 Large-Ring Heterocycles from β-Lactams	491	(1)
20.6 Concluding Remarks and Prospects	492	(1)
References	493	(4)
21. Multiple-Component Condensation Methods for Preparation of Combinatorial Libraries of β-Amino Carbonyl Derivatives	497	(30)
James C. Adrian, Jr.
21.1 Introduction	497	(3)
21.2 Mannich Reaction	500	(13)
21.3 Other Multiple-Component Reactions	513	(7)
21.4 Solid-Phase MCC Methods	520	(1)
21.5 Conclusions	521	(2)
References	523	(4)
22. Using Constrained β-Amino Acid Residues to Control β-Peptide Shape and Function	527	(66)
Michael A. Gelman and Samuel H. Gellman
22.1 Introduction: β-Peptides in the Foldamer Context	527	(4)
22.2 Monomer Synthesis	531	(26)
22.3 β-Peptide Synthesis	557	(5)
22.4 Conformational Data	562	(14)
22.5 Biological Applications	576	(8)
22.6 New Frontiers for β-Peptide Structure	584	(1)
References	585	(8)
23. β²-Amino Acids with Proteinogenic Side Chains and Corresponding Peptides: Synthesis, Secondary Structure, and Biological Activity	593	(26)
Marino A. Campo, Jaime Ewa/ante, and Radovan Šehesta
23.1 Introduction	593	(1)
23.2 Synthesis of β²-Amino Acids	594	(9)
23.3 Solution and Solid-Phase Synthesis of Peptides Containing β²-Amino Acids	603	(2)
23.4 Secondary Structures of Peptides Containing β²-Amino Acids	605	(6)
23.5 Biologically Active Peptides Containing Proteinogenic β²-Amino Acids	611	(3)
23.6 Conclusions	614	(1)
Abbreviations	614	(1)
References	614	(5)
Index	619