Silver‐Catalyzed Carbene, Nitrene, and Silylene Transfer Reactions

Abstract

Carbene insertion into N-H bonds is typically catalyzed by copper and dinuclear rhodium complexes. This chapter presents examples of silver-catalyzed nitrene transfers encompassing the general classes of transformations, with an emphasis on chemistry reported since 2008. It highlights the features of silver catalysis that have enabled recent advances in nitrene transfer over the past ten years. Descriptions of the underlying design principles are included with the intent of inspiring and enabling the design of increasingly selective amination reactions based on silver, particularly in the realm of asymmetric C-N bond formation. There are a variety of nitrogen sources that have been employed in metal-catalyzed nitrene transfer. Silver-catalyzed silylene transfers into C-O bonds are also prevalent in the literature. One such example, reported by Woerpel and coworkers, involves the silver-catalyzed insertion of silylenes into vinyl epoxides to prepare allylic silanes as key intermediates.