Nitrenium ions as new versatile reagents for electrophilic amination

Abstract

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 N-alkyl and N-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. Furthermore, we present the facile synthesis of valuable ¹⁵N-labelled primary amines from easily prepared ¹⁵N-labelled nitrenium salts, as well as a one-pot approach to biologically relevant primary amines. Finally, a recyclable variant of the nitrenium precursor was prepared and a simple recovery protocol was developed to improve the atom-economy of this procedure.