Redox Self‐Adaptation of a Nitrene Transfer Catalyst to the Substrate Needs

Abstract

Abstract The development of iron catalysts for carbon–heteroatom bond formation, which has attracted strong interest in the context of green chemistry and nitrene transfer, has emerged as the most promising way to versatile amine synthetic processes. A diiron system was previously developed that proved efficient in catalytic sulfimidations and aziridinations thanks to an Fe III Fe IV active species. To deal with more demanding benzylic and aliphatic substrates, the catalyst was found to activate itself to a Fe III Fe IV L . active species able to catalyze aliphatic amination. Extensive DFT calculations show that this activation event drastically enhances the electron affinity of the active species to match the substrates requirements. Overall this process consists in a redox self‐adaptation of the catalyst to the substrate needs.