Mechanistic and chemoselective investigations on nitrene transfer reactions mediated by a novel iron-mesoionic carbene catalyst

The mesoionic carbene iron complex is a new catalyst, and its catalytic mechanisms for the nitrene transfer reactions were investigated via density functional theory calculations. Especially, the amination-to-aziridination chemoselectivity is predicted for the first time. The origin of the chemoselectivity toward C(sp3)–H amination has been revealed. Based on our calculated results, it can be suggested that the substrate scope of this novel catalytic system may be expanded to alkenes to greatly broaden its potential applications in constructing N-heterocyclic compounds.