Phosphorus Derivatives of Hydroxylamines, Oximes and Hydroxamic Acids

Abstract

AbstractThis comprehensive chapter, organized in three different sections, includes new topics focused on preparation and synthetic applications of phosphorus functionalized hydroxylamines, oximes and hydroxamic acids. The first section comprises the synthesis of phosphorusO‐substituted hydroxylamines either through phosphorus‐oxygen or nitrogen‐oxygen single bond formation. The synthesis ofN‐substituted hydroxylamines is also covered in this first section by means of phosphorus‐nitrogen or carbon‐nitrogen bond formation reactions. This section also includes several transformations of phosphorus substituted hydroxylamines including among others: rearrangement, hydrolysis, reduction and oxidation reactions. Functionalized oximes containing phosphorus substituents includingO‐ andC‐substituted oximes, and oximes with α‐ and β‐phosphorated moieties are covered in a second section. This provides an introduction to the common approaches to synthesize phosphorus substituted oximes, and the application of phosphorated oximes to the preparation of more elaborated compounds have been described. Some of the synthetic applications methods covered in the second section are fragmentation and rearrangement reactions, nucleophilic substitution at the phosphorus atom, intramolecular reactions, radical reactions, reduction of carbon‐nitrogen double bond, oxidation reactions, olefination reactions, dehydratation of oximes. The third section is dedicated to the synthesis and reactivity of phosphorusO‐,N‐, andC‐substituted hydroxamic acid derivatives, spanning the few reports in the literature covering this topic. An extensive and current list of references and a subject index complete the chapter.Phosphorus Substituted Hydroxylamine DerivativesPhosphorus Substituted OximesPhosphorus Substituted Hydroxamic Acid DerivativesAcknowledgments