The oxidation of N-benzylaziridine catalyzed by iron porphyrin: Radical versus electron transfer mechanism

A change in the mechanism of biomimetic oxidation of tertiary amines in res ponse to appropriate structural features of the substrate, emerges from the investigation of the product pattern from N-benzylaziridine under bona fid e radical or electron transfer conditions. This substrate is an amine endow ed with a high oxidation potential as a result of steric constraint. Conseq uently, the hydrogen atom transfer route of oxidative N-dealkylation compet es favorably with the electron transfer route, which is the mechanism obser ved for the reaction of conventional tertiary amines with metalloporphyrins and oxygen donors.