Functional-Group-Tolerant, Silver-Catalyzed N–N Bond Formation by Nitrene Transfer to Amines

Abstract

Silver(I) promotes the highly chemoselective N-amidation of tertiary amines under catalytic conditions to form aminimides by nitrene transfer from PhI=NTs. Remarkably, this transformation proceeds in a selective manner in the presence of olefins and other functional groups without formation of the commonly observed aziridines or C-H insertion products. The methodology can be applied not only to rather simple tertiary amines but also to complex natural molecules such as brucine or quinine, where the products derived from N-N formation were exclusively formed. Theoretical mechanistic studies have shown that this selective Namidation reaction proceeds through triplet silver-nitrenes.