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

Identifier:  imarina:3654708

Handle: https://hdl.handle.net/20.500.11797/imarina3654708

Authors:  Maestre, L; Dorel, R; Pablo, O; Escofet, I; Sameera, WMC; Alvarez, E; Maseras, F; Díaz-Requejo, MM; Echavarren, AM; Pérez, PJ

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 bond formation were exclusively formed. Theoretical mechanistic studies have shown that this selective N-amidation reaction proceeds through triplet silver nitrenes.