Amino Acid Derivatives A Practical Approach

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Edition: 1st
Format: Hardcover
Pub. Date: 2000-03-16
Publisher(s): Oxford University Press
List Price: $239.99

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Summary

Many successful syntheses of homochiral organic compounds use an amino acid derivative as a starting point. Such syntheses are not confined to peptides as targets; peptide synthesis strategies have been narrowed down to a few well-defined protocols (and these are not covered in this book).Outside the peptide field, many non-routine syntheses have been established that give the intended products in which the structural features of the starting amino acid are barely recognisable. This book is a laboratory guide that covers the early stages of syntheses under these headings, whichinvariably call for modifications to the functional groups of readily-available L-amino acids. It will therefore give invaluable guidance to the preparation of amino acid derivatives to be used not only in these broad area of synthesis but also in amino acid analysis. Synthetic work with aminoacids carried out by new users and by experienced chemists and other scientists, will be supported by the detailed practical protocols and background information provided in this book.

Table of Contents

List of contributors
xiii
Abbreviations xv
Introduction
1(6)
Graham C. Barrett
The L-α-amino acids
1(1)
The β-amino acids, the γ-amino acids, etc.
1(1)
Amino acids with side-chain functional groups
2(1)
Mechanistic details of reactions with amino acids
2(1)
Practical details provided in this book
2(2)
Nomenclature
4(1)
Safety considerations
4(3)
Acylation and alkoxycarbonylation of the amino group
7(14)
Graham C. Barrett
Introduction
7(1)
N-Acylation and N-alkoxycarbonylation
7(1)
Purification of products of acylation of amino acids
8(3)
N-Benzyloxycarbonyl-L-amino acids
11(5)
N-tert-Butoxycarbonylation of sterically hindered α-amino acids
16(5)
References
18(3)
Thioacylation of the amino group of an amino acid
21(6)
Graham C. Barrett
General
21(1)
Content of this chapter
22(1)
Cyclization of N-thioacylamino acids to 2, 4-disubstituted thiazol-5(4H)-ones---racemization of L-and D-amino acids
23(4)
References
24(3)
Mono- and di-alkylation of the amino group
27(6)
Graham C. Barrett
Preparations from N-protected amino acids
27(3)
Preparation by reduction of Schiff bases
30(1)
N,N-Dibenzylamino acid benzyl esters
31(2)
References
32(1)
Reactions at the carboxy group of an amino acid---amino acid salts
33(4)
Graham C. Barrett
Introduction
33(1)
Solubility of amino acids in water and in organic solvents---preparation of an organic salt of an amino acid
33(4)
References
35(2)
Reactions at the carboxy group of an amino acid---esterification of amino acids
37(14)
Graham C. Barrett
Introduction
37(1)
Standard esterification protocols
38(6)
Aryl and heteroaryl esters of N-protected amino acids
44(3)
2-Phenylthiazol-5-yl esters of N-protected amino acids
47(4)
References
48(3)
Carboxy group modifications---synthesis of a homochiral ketone derived from L-tryptophan
51(22)
Kevin J. Merchant
Introduction
51(1)
Synthetic strategy
51(6)
Ketones derived from amino acids
57(6)
The Horner-Wadsworth-Emmons reaction
63(3)
Reduction of α,β-unsaturated ketones to saturated ketones
66(2)
Deprotection of the amino ketone
68(5)
References
71(2)
Synthons derived from aspartic and glutamic acids
73(28)
Mark G. Moloney
Introduction
73(1)
Glutamic acid
73(5)
Pyroglutamic acid
78(5)
Pyroglutaminol
83(10)
Aspartic acid
93(8)
References
98(3)
Benzophenone Schiff bases of α-amino acid esters as electrophiles. Addition of Grignard reagents and alkyllithiums to produce threo-amino alcohols and amino polyols
101(14)
Robin L. Polt
Introduction
101(1)
Preparation of benzophenone Schiff bases
102(3)
Tandem reduction and alkylation of the Schiff base esters
105(6)
Synthesis of more complex amino polyols
111(4)
References
113(2)
Synthetic uses of serine, threonine and cysteine
115(18)
Patrick Meffre
Liliane Vo-Quang
Yen Vo-Quang
Francois Le Goffic
Introduction
115(2)
Acetonide protection of L-serine, L-threonine and L-cysteine
117(6)
Reduction of L-serine-, L-threonine-and L-cysteine-derived acetonide esters
123(10)
References
129(4)
Synthetic uses of methionine
133(12)
Patrick Meffre
Liliane Vo-Quang
Yen Vo-Quang
Francois Le Goffic
Introduction
133(1)
Synthesis of N-(benzyloxycarbonyl)-L-vinylglycine methyl ester from L-methionine methyl ester hydrochloride
134(5)
Synthesis of L-aspartic β-semialdehyde
139(6)
References
142(3)
Metal-mediated modification of the side-chains of α-amino acids
145(40)
Geoffrey T. Crisp
Introduction
145(1)
Coupling reactions
146(35)
Conclusion
181(4)
References
182(3)
Diastereocontrolled functionalization of enantiomerically pure 5-phenyl-1,4-oxazin-2-ones by azomethine ylid generation and trapping
185(48)
L. M. Harwood
I. A. Lilley
G. G. Cox
C. E. Williams
Construction of 1,4-oxazin-2-ones
185(20)
Diastereocontrolled functionalization of 1,4-oxazin-2-one templates via azomethine ylid generation and dipolar cycloaddition reactions
205(17)
Hydrogenolytic cleavage of the 1,4-oxazin-2-one template and liberation of the free amino acids
222(11)
References
229(4)
Reductive modifications of the carboxy group
233(10)
Graham C. Barrett
Introduction
233(6)
Swern oxidation of primary β-aminoalkanols to α-amino aldehydes
239(4)
References
241(2)
Reactions at the α-carbon atom of α-amino acid derivatives
243(4)
Graham C. Barrett
Introduction
243(1)
Acidity of α-amino acids; racemization of L-α-amino acids
243(2)
α,β-Elimination from protected α-amino acids giving protected α-aminoacrylic acids
245(2)
References
246(1)
Modifications of the aryl substituents of β-aryl α-amino acids
247(6)
Graham C. Barrett
General
247(1)
Tyrosinase (alias polyphenol oxidase, monophenol oxidase, EC 1.14.18.1)
247(6)
References
252(1)
Isolation and chromatographic purification of reaction products from amino acids
253(8)
Ian A. O'Neil
Introduction
253(1)
Reversed-phase dry flash chromatography
253(8)
References
259(2)
List of suppliers 261(6)
Index 267

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