Photocatalytic Benzylation of C(sp ³ )–H Bonds with Alcohol Derivatives via Radical–Radical Cross-Couplings

We have developed a versatile photocatalytic platform for the direct benzylation of diverse C(sp 3 )–H bonds using N -acyl carbamothioates derived from readily available alcohols as benzyl radical precursors. This protocol operates through two complementary manifolds: a consecutive photoinduced electron transfer (Con-PET) process for the benzylation of N -α-C(sp 3 )–H bonds and a thiol-mediated hydrogen atom transfer (HAT) cycle for more challenging substrates including alkenes, ethers, thioethers and toluenes. This deoxygenative strategy enables efficient C(sp 3 )–C(sp 3 ) radical–radical cross-coupling without transition-metal-coupling catalysts, external oxidants, or radical stabilizers, delivering the desired products in moderate to good yields (up to 70%).