7.02 Oxidation by Metals (Nitrene)

Abstract

Recent surge of interest in metal-catalyzed nitrene transfer reactions reflects the high importance of such reactions in organic synthesis. Nitrene transfer reaction, the analogous to carbene and oxo transfer reactions, involves the formation of a new covalent X–N bond, where X is mainly C atom for most of the metal-catalyzed nitrene transfer and insertion reactions. This class of reactions can also be viewed as oxidation due to the higher electronegativity of nitrogen atom than carbon atom. In this chapter, the focus is on the transition metal-catalyzed nitrene transfer and insertion reactions reported since the year 2000. A brief description of earlier studies is provided. Mechanistic studies including the preparation and characterization of the reaction intermediates and the identification of short-lived reactive species are discussed. The recent important findings in transition metal-catalyzed alkene aziridination, C–H amidation/amination, and sulfimidation reactions are highlighted in this chapter.