Amino Acids: Insights and Roles in Heterocyclic Chemistry, Volume 4: Azlactones and Oxazolidin-5-ones 4

This first-of-its-kind four-volume book series provides up-to-date information on α-amino acids, detailing the potential challenges in working with α-amino acids, the protecting groups for the carboxyl, side chain groups of the amino acids, and the most popular heterocyclic compounds that are originating from α-amino acids. These heterocyclic compounds include hydantoins, thiohydantoins (including 2-thiohydantoins, 4-thiohydantoins, 2,4-dithiohydantoins), 2,5-diketopiperazines, N-carboxyanhydrides, N-thiocarboxyanhydrides, sydnones, sydnonimines, azlactones, pseudoazlactones, and oxazolidin-5-ones. This is the first resource to comprehensively present all the heterocycles that can be directly prepared from α-amino acids. In addition, almost all kinds of synthetic methods for a particular type of heterocycles from α-amino acids are included, along with the detailed mechanistic discussions and experimental procedures. Volume 4: Azlactones and Oxazolidin-5-ones discusses two types of simple heterocycles that can be prepared from α-amino acids, i.e., azlactones (also known as oxazolones, 4-unsaturated azlactones included) and oxazolidin-5-ones. These heterocyclic compounds behave differently in both biological and chemical properties, and their biological activities are presented in a well-organized manner in this volume. The other volumes in the set are: Volume 1: Protecting Groups Volume 2: Hydantoins, Thiohydantoins, and 2,5-Diketopiperazines Volume 3: N-Carboxyanhydrides, N-Thiocarboxyanhydrides, and Sydnones All together, this unique 4-volume set thoroughly covers the two types of heterocyclic compounds that are originated from alpha-amino acids, providing carefully compiled updated information with detailed examples. The author has shared many thoughtful insights based on his strong background in physical organic chemistry. The volumes will be highly valuable for graduate students and senior students, as well as for professors and researchers working in the field of medicinal and pharmaceutical chemistry, organic chemistry, organic synthesis, heterocycles, and proteins and peptides. Cover Half Title Amino Acids: Insights and Roles in Heterocyclic Chemistry Series Amino Acids: Insights and Roles in Heterocyclic Chemistry, Volume 4: Azlactones and Oxazolidin-5-ones Copyright About the Editors Contents Abbreviations Acknowledgments Preface Preface for Amino Acids: Insights and Roles in Heterocyclic Chemistry 1. Azlactones 1.1 Introduction 1.2 Biological Activities 1.3 Preparative Methods 1.3.1 Preparation of Unsaturated Azlactones 1.3.1.1 Erlenmeyer Azlactone Synthesis 1.3.1.1.1 Erlenmeyer Azlactone Synthesis Under Basic Conditions 1.3.1.1.2 Erlenmeyer Azlactone Synthesis Under Neutral Conditions 1.3.1.1.3 Erlenmeyer Azlactone Synthesis Under Acidic Conditions 1.3.1.2 Alternative Methods for the Preparation of Unsaturated Azlactones 1.3.1.3 Configuration of the Exocyclic Double Bond in Unsaturated Azlactones 1.3.2 Preparation of Saturated Azlactones 1.3.3 Mechanisms for the Formation of Azlactones 1.4 Reactions 1.4.1 Chemical Reactivities of Saturated Azlactones 1.4.1.1 Reactions AT C2 of Azlactones 1.4.1.2 Reactions AT C4 of Azlactones 1.4.1.2.1 Alkylation of Azlactones 1.4.1.2.2 Allylic Alkylation of Azlactones 1.4.1.2.3 Benzylation of Azlactones 1.4.1.2.4 Arylation of Azlactones 1.4.1.2.5 Carboxylation of Azlactones, the Steglich Rearrangement 1.4.1.2.6 Acylation of Azlactones 1.4.1.2.7 Alkynylation of Azlactones 1.4.1.2.8 Aldol Condensation of Azlactones 1.4.1.2.9 Mannich Reaction 1.4.1.2.10 Michael Reaction 1.4.1.2.11 Addition to Isolated Alkenes or Ene Reactions 1.4.1.2.12 Addition to Alkynes 1.4.1.2.13 Addition to Diazo Compounds 1.4.1.2.14 Addition to Allenes 1.4.1.2.15 Miscellaneous Reactions at C4 of Azlactones 1.4.1.3 Reactions AT C5 of Azlactones 1.4.1.3.1 Reactions with Amines 1.4.1.3.2 Reactions with Alcohols 1.4.1.3.3 Reactions with Thiols 1.4.1.3.4 Reactions with Oximes 1.4.1.3.5 Miscellaneous Reactions at C5 of Azlactones 1.4.1.4 Cycloadditions 1.4.1.4.1 1,3-Dipolar Cycloaddition 1.4.1.4.2 [4+2] Cycloaddition 1.4.1.4.3 [8+2] Cycloaddition 1.4.2 Chemical Reactivities of Unsaturated Azlactones 1.4.2.1 Nucleophilic Vinylogous Reactivity of Olefinic Azlactones 1.4.2.2 Vinylogous Arylation of Azlactones 1.4.2.3 Reactions of Unsaturated Azlactones with Carbon Nucleophiles 1.4.2.4 Nucleophilic Addition of Benzimidamide to Unsaturated Azlactones 1.4.2.5 The Reaction of Unsaturated Azlactones with Water 1.4.2.6 The Reaction of Unsaturated Azlactones with Amines 1.4.2.7 Azidolysis of Unsaturated Azlactones 1.4.2.8 Reaction of Hydrazine with Unsaturated Azlactones 1.4.2.9 The Reaction of Alcohols or Thiols with Unsaturated Azlactones 1.4.2.10 Oxygenation of Unsaturated Azlactones 1.4.2.11 1,3-Dipolar Cycloaddition with Exocyclic Double Bond of Unsaturated Azlactones 1.4.2.12 [4+2] Cycloaddition with Exocyclic Double Bond of Unsaturated Azlactones 1.4.2.13 Cyclopropanation of Unsaturated Azlactones 1.4.2.14 Photodimerization of Unsaturated Azlactones 1.4.2.15 Miscellaneous Reaction of Unsaturated Azlactones 1.5 Applications 1.6 Pseudoazlactones 1.7 Final Comments Keywords References 2. Oxazolidin-5-ones 2.1 Introduction 2.2 Natural Occurrence 2.3 Biological Activities 2.3.1 Antibacterial and Antimicrobial Activities 2.3.2 Anticancer Activity and Cleavage of DNA 2.3.3 Signal Molecules 2.4 Preparative Methods 2.4.1 Preparation of Oxazolidin-5-Ones from α-Amino Acid Derivatives and Formaldehyde 2.4.2 Preparation of Oxazolidin-5-Ones from α-Amino Acid Derivatives and Acetaldehyde 2.4.3 Preparation of Oxazolidin-5-Ones from α-Amino Acid Derivatives and Benzaldehyde 2.4.4 Preparation of Oxazolidin-5-Ones from α-Amino Acid Derivatives and Pivalaldehyde (t-BuCHO) 2.4.5 Preparation of Oxazolidin-5-Ones from α-Amino Acid Derivatives and Other Aldehydes 2.4.6 Preparation of Oxazolidin-5-Ones from α-Amino Acid Derivatives and Acetone 2.4.7 Preparation of Oxazolidin-5-Ones from α-Amino Acid Derivatives and Hexafluoroacetone 2.4.8 Preparation of Oxazolidin-5-Ones from α-Amino Acid Derivatives and Other Ketones 2.4.9 Preparation of Oxazolidin-5-Ones from α-Amino Acid Derivatives and Alternative Compounds 2.5 Reactions of Oxazolidin-5-Ones 2.5.1 Oxazolidin-5-Ones in Alkylation AT C-4 2.5.2 Formation of N-Methyl Amino Acids 2.5.3 Oxazolidin-5-Ones in Nucleophilic Addition 2.5.4 Decarboxylation to Mesoionic Species for 1,3-Dipolar Cycloaddition 2.5.5 Proline Catalyzed Reactions 2.5.6 Temporary Protection of α-Amino and Carboxyl Groups 2.5.7 Preparation of Peptides 2.5.8 Reactions Occurring AT C5 of Oxazolidin-5-Ones 2.5.9 Miscellaneous Reaction of Oxazolidin-5-Ones 2.6 Applications Keywords References Index "This first-of-its-kind four-volume book series, Amino Acids: Insights and Roles in Heterocyclic Chemistry, provides readers with up-to-date information on alpha-amino acids, the potential challenges in working with alpha-amino acids, the protecting groups for the carboxyl, amino and side chain groups of the amino acids, and the most popular heterocyclic compounds that are originating from alpha-amino acids. These heterocyclic compounds include hydantoins, thiohydantoins (including 2-thiohydantoins, 4-thiohydantoins, 2,4-dithiohydantoins), 2,5-diketopiperazines, N-carboxyanhydrides, N-thiocarboxyanhydrides, sydnones, sydnonimines, azlactones, pseudoazlactones, and oxazolidin-5-ones. This is the first resource to comprehensively collect all the heterocycles that can be directly prepared from alpha-amino acids. In addition, almost all kinds of synthetic methods for a particular type of heterocycles from alpha-amino acids are include, along with the detailed mechanistic discussions and experimental procedures. Volume 1: Protecting Groups, the first volume of this set, has collected the 260 protecting groups relating to amino acids, which have been organized by carboxyl group, amino group, and side chain group. The conditions to introduce these protecting groups as well as their deprotecting procedures have also been incorporated, along with the physical properties, solvent effect and temperature effect on the solubility of amino acids. It presents the solubility of glycine and phenylalanine in a variety of solvent systems to show the impact of solvent on the solubility of amino acid, where glycine generally represents the polar amino acid whereas phenylalanine represents the amino acid of non-polar side chain."-- Provided by publisher This first-of-its-kind four-volume book series, Amino Acids: Insights and Roles in Heterocyclic Chemistry, provides readers with up-to-date information on alpha-amino acids, the potential challenges in working with alpha-amino acids, the protecting groups for the carboxyl, amino and side chain groups of the amino acids, and the most popular heterocyclic compounds that are originating from alpha-amino acids. These heterocyclic compounds include hydantoins, thiohydantoins (including 2-thiohydantoins, 4-thiohydantoins, 2,4-dithiohydantoins), 2,5-diketopiperazines, N-carboxyanhydrides, N-thiocarboxyanhydrides, sydnones, sydnonimines, azlactones, pseudoazlactones, and oxazolidin-5-ones. This is the first resource to comprehensively collect all the heterocycles that can be directly prepared from alpha-amino acids. In addition, almost all kinds of synthetic methods for a particular type of heterocycles from alpha-amino acids are include, along with the detailed mechanistic discussions and experimental procedures. Volume 4: Azlactones and Oxazolidin-5-ones discusses two types of simple heterocycles that can be prepared from alpha-amino acids, i.e., azlactones (also known as oxazolones, 4-unsaturated azlactones included) and oxazolidin-5-ones. These heterocyclic compounds behave differently in both biological and chemical properties, and their biological activities are presented in a well-organized manner in this volume