Aziridination of inert alkanes via photo-mediated double hydrogen atom transfer

The direct functionalization of inert alkanes is a longstanding challenge in synthetic chemistry due to the high bond dissociation energy of C(sp3)–H bonds. Hydrogen atom transfer (HAT) has emerged as a powerful strategy for mono-functionalization, while the development of methods enabling vicinal double functionalization of alkanes remains limited and typically relies on a monofunctionalization–β-elimination–difunctionalization cascade. We have developed an unprecedented double-HAT process, leveraging the unique reactivity of photo-generated triplet sulfonyl nitrenes under visible-light irradiation, to directly transform inert alkanes into aziridines. This novel approach streamlines the synthesis of diverse aziridines from readily available alkanes, assisted by a high-speed circulation flow platform for large-scale synthesis. Mechanistic insights, supported by both experimental and computational investigations, reveal the formation of an olefin intermediate through a double-HAT process, with the in-situ generated triplet sulfonyl nitrenes and iodosobenzene playing critical roles in the reaction pathway.