Photoredox-catalyzed C( sp 3 )─H radical functionalization to enable asymmetric synthesis of α-chiral alkyl phosphine

α-Chiral alkyl phosphines are privileged structural motifs with a wide application in organic and medical synthesis. It is highly desirable to develop stereoselective methods to prepare these enantioenriched molecules. The incorporation of C( sp 3 )─H functionalization and chiral phosphine chemistry is much less explored, probably because of the weak reactivity of C( sp 3 )─H bonds and/or the challenging site- and stereoselectivity issues. Herein, we disclose a synergistic catalysis system to enable an enantioselective radical addition process of α-substituted vinylphosphine oxides. An array of diverse α-chiral alkyl phosphors compounds is smoothly accessed by using the readily available chemicals as the inert C( sp 3 )─H bond reagent, such as sulfides, amines, alkenes, and toluene derivatives, exerting remarkable chemo-, site-, and enantioselectivity. On the basis of the mechanistic studies, both the C( sp 3 )─H bond activation and the stereochemistry-determining step are proposed to involve a single-electron transfer/proton transfer process.