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

• DOI: 10.1021/jacs.6b08219
• Publication Date: 2017-01-18T20:53:51Z
• Authors: Lourdes Maestre; Ruth Dorel; Óscar Pablo; Imma Escofet; W. M. C. Sameera; Eleuterio Álvarez; Feliu Maseras; M. Mar Díaz-Requejo; Antonio M. Echava...; Pedro J. Pérez
• Keywords: Nitrene; Functional group; Brucine

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 presence olefins and other functional groups without formation commonly observed aziridines or C-H insertion products. The methodology can be applied not only rather simple but also complex natural molecules such as brucine quinine, where products derived N-N bond were exclusively formed. Theoretical mechanistic studies have shown that reaction through triplet silver nitrenes.