Accessing Aerial Transformation of Arylmethanamines into Amides Using a Redox-Active Aryl-Substituted BIAN-Based Catalyst

Abstract

The direct α-oxygenation of arylmethanamines to amides is a cornerstone transformation in organic synthesis; however, traditional methods suffer from harsh conditions, reactive reagents, and expensive transition metal catalysts. This study introduces a novel approach using a redox-active aryl-substituted bis(imino)acenaphthene (Ar-BIAN)-based organic radical anion as a catalyst that mimics transition metal catalysis in the aerial oxidation of arylmethanamines into their corresponding amides for the first time. This protocol showcases a wide substrate scope along with tolerance of common organic functional groups. Through various experiments and theoretical calculations, a plausible mechanism has been proposed, involving dehydrogenation of amine to nitrile and its subsequent hydrolysis to amide.