Modular Iminophosphorane as Hydrogen Atom Transfer Catalyst for Selective C(sp3)–H Functionalization

Iminophosphoranes, readily accessed via the Staudinger reaction, have been developed as tunable hydrogen atom transfer catalysts that override thermodynamic C(sp3)–H bond-strength preferences. Under acridinium photoredox catalysis, selective C(sp3)–H alkylation proceeds across diverse substrates, and systematic modulation of phosphorus and nitrogen substituents enables the tunable enhancement of regioselectivity for sterically accessible secondary or primary positions.