Visible-Light-Driven Palladium-Catalyzed Radical Alkylation of C-H Bonds with Unactivated Alkyl Bromides

Reported herein is a novel visible-light photoredox system with Pd(PPh3)(4) as the sole catalyst for the realization of the first direct cross-coupling of C(sp(3))-H bonds in N-aryl tetrahydroisoquinolines with unactivated alkyl bromides. Moreover, intra- and intermolecular alkylations of heteroarenes were also developed under mild reaction conditions. A variety of tertiary, secondary, and primary alkyl bromides undergo reaction to generate C(sp(3))-C(sp(3)) and C(sp(2))-C(sp(3)) bonds in moderate to excellent yields. These redox-neutral reactions feature broad substrate scope (>60 examples), good functional-group tolerance, and facile generation of quaternary centers. Mechanistic studies indicate that the simple palladium complex acts as the visible-light photocatalyst and radicals are involved in the process.