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

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.