Metal-free direct alkylation of unfunctionalized allylic/benzylic sp3 C–H bonds via photoredox induced radical cation deprotonation† †Electronic supplementary information (ESI) available: Experimental procedures, characterization data and NMR spectra of all new compounds; ORTEP drawing of compound 41 (major diastereomer). CCDC 1506724. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc00953d Click here for additional data file. Click here for additional data file.

Despite notable recent efforts, a catalytic and convenient strategy for the direct alkylation of unactivated allylic or benzylic sp C–H bonds remains a formidable challenge facing the synthesis community. We herein report an unprecedented allylic/benzylic alkylation using only an organo-photoredox catalyst, which enables coupling of a broad scope of alkenes/arenes and electron-deficient alkenes in an atomand redox-economic manner. A photoredox induced alkene/arene radical cation deprotonation is proposed to smoothly generate the key allylic and benzylic radical intermediates. It represents the first C–C bond formation via radical cation deprotonation under visible light conditions. The resulting products can be easily scaled up and directly converted to g,d-unsaturated or a,b-diaryl-acids, -esters, -amides, -pyrazoles, -isoxazoles, as well as lactones, which enables this mild and selective sp C–H alkylation to rapidly access complex bioactive molecules.