Photoredox/Copper-Cocatalyzed Difluoromethylation of Benzylic Bromides with PPh ₃ (CF ₂ H) ₂

We describe a general copper/photoredox-cocatalyzed difluoromethylation of benzyl bromides using PPh 3 (CF 2 H) 2 as a reagent. This protocol exhibits a broad substrate scope, good yields, and high functional group compatibility. The Cu(I) species first activates the benzylic C–Br bond to form a benzyl radical and then scavenges a CF 2 H radical to form a Cu(III) species. The facile reductive elimination from the Cu(III) center enables the coupling of the CF 2 H radical with the C(sp 3 ) fragment.