Nitrenium ions as new versatile reagents for electrophilic amination.

Herein we report the utilization of N-heterocyclic nitrenium ions - easily prepared, bench-stable and non-oxidating nitrogen sources for the efficient electrophilic amination of aliphatic and aromatic organometallic nucleophiles, towards the facile and general preparation of primary amines. To this end, a plethora of abundant organolithium and organomagnesium reagents were combined with nitrenium salts to generate a variety of previously unexplored -alkyl and -aryl triazanes. Through the simple hydrogenolysis of these relatively stable triazanes, we have prepared a diverse scope of primary amines, including linear and branched aliphatic as well as (hetero)aromatic amines possessing various stereo-electronic substituents.