Z705276
Sigma
Chemistry of Peptide Synthesis
| ISBN-10: | 1-57444454-9 |
| ISBN-13: | 978-1-57444454-4 |
Description
| General description | This is an overview of how peptides are synthesized and what techniques are likely to generate the most desirable reactions. The author first outlines the fundamentals of peptide synthesis, focusing on the intermediates in aminolysis reactions. It then builds into discussions of the applicability of coupling reactions, stereomutation, methods of deprotection, solid-phase synthesis, side-chain protection and side reactions, and amplification on coupling methods. It clarifies the differences between oxazolones from amino-acid derivatives and segments and the implications of their formation on the chiral integrity of products. The author offers a critical analysis of the mechanisms of coupling reactions and the desirability of preactivation. The text explains hindrance and the nucleophilicity of tertiary amines and rationalizes their use. It also explores mechanisms of acidolysis and the dual role of nucleophiles as reactants and scavengers. |
Properties
| publication info | N. Benoiton, CRC Press, 2005, 304 pp., hard cover |
Table Of Contents
| Table of Contents | PARTIAL FUNDAMENTALS OF PEPTIDE SYNTHESIS Chemical and Stereochemical Nature of Amino Acids Ionic Nature of Amino Acids Charged Groups in Peptides at Neutral pH Side-Chain Effects in Other Amino Acids General Approach to Protection and Amide-Bond Formation N-Acyl and Urethane-Forming N-Substituents METHODS FOR THE FORMATION OF PEPTIDE BONDS Coupling Reagents and Methods and Activated Forms Peptide-Bond Formation from Carbodiimide-Mediated Reactions of N-Alkoxycarbonylamino Acids Factors Affecting the Course of Events in Carbodiimide-Mediated Reactions of N-Alkoxycarbonylamino Acids Intermediates and Their Fate in Carbodiimide-Mediated Reactions of N-Alkoxycarbonylamino Acids Peptide-Bond Formation from Preformed Symmetrical Anhydrides of N-Alkoxycarbonylamino Acids Peptide-Bond Formation from Mixed Anhydrides of N-Alkoxycarbonylamino Acids PROTECTORS AND METHODS OF DEPROTECTION The Nature and Properties Desired of Protected Amino Acids Alcohols from which Protectors Derive and Their Abbreviated Designations Deprotection by Reduction: Hydrogenolysis Deprotection by Reduction: Metal-Mediated Reactions Deprotection by Acidolysis: Benzyl-Based Protectors Deprotection by Acidolysis:tert-Butyl-Based Protectors CHIRALITY IN PEPTIDE SYNTHESIS Mechanisms of Stereomutation: Acid-Catalyzed Enolization Mechanisms of Stereomutation: Base-Catalyzed Enolization Enantiomerization and Its Avoidance during Couplings of N-Alkoxycarbonyl-L-Histidine Mechanisms of Stereomutation: Base-Catalyzed Enolization of Oxazolones Formed from Activated Peptides Mechanisms of Stereomutation: Base-Induced Enolization of Oxazolones Formed from Activated N-Alkoxycarbonylamino Acids Stereomutation and Asymmetric Induction SOLID-PHASE SYNTHESIS The Idea of Solid-Phase Synthesis Solid-Phase Synthesis as Developed by Merrifield Vessels and Equipment for Solid-Phase Synthesis A Typical Protocol for Solid-Phase Synthesis Features and Requirements for Solid-Phase Synthesis Options and Considerations for Solid-Phase Synthesis REACTIVITY, PROTECTION, AND SIDE REACTIONS Protection Strategies and the Implications Thereof Constitutional Factors Affecting the Reactivity of Functional Groups Constitutional Factors Affecting the Stability of Protectors The e-Amino Group of Lysine The Hydroxyl Groups of Serine and Threonine Acid-Induced O-Acylation of Side-Chain Hydroxyls and the O-to-N Acyl Shift VENTILATION OF ACTIVATED FORMS AND COUPLING METHODS Notes on Carbodiimides and Their Use Cupric Ion as an Additive that Eliminates Epimerization in Carbodiimide-Mediated Reactions Mixed Anhydrides: Properties and Their Use Secondary Reactions of Mixed Anhydrides: Urethane Formation Decomposition of Mixed Anhydrides: 2-Alkoxy-5(4H)-Oxazolone Formation and Disproportionation Activated Esters: Reactivity MISCELLANEOUS Enantiomerization of Activated N-Alkoxycarbonylamino Acids and Esterified Cysteine Residues in the Presence of Base Options for Preparing N-Alkoxycarbonylamino Acid Amides and 4-Nitroanilides Options for Preparing Peptide Amides Aggregation during Peptide-Chain Elongation and Solvents for its Minimization Alkylation of Peptide Bonds to Decrease Aggregation: 2-Hydroxybenzyl Protectors APPENDICES |
