Photocatalytic redox-neutral arylation of cyclopropanols with cyanoarenes via radical-mediated C–C and C–CN bond cleavage

β-Arylated ketones widely exist in many biologically active molecules and natural products. Herein, we describe a photocatalytic redox-neutral arylation of cyclopropanols with cyanoarenes via radical-mediated C–C and C–CN bond cleavage to afford various β-arylated ketones. This mild and external oxidant-free approach showed good compatibility with a range of cyclopropanols and cyanoarenes and accomplished absolute regioselective control for the precise functionalization of pyridines via the C–CN bond cleavage of 4-cyanopyridines. Remarkably, this photocatalytic ring-opening of cyclopropanols was enabled by proton-coupled electron transfer (PCET) activation using an oxidized photocatalyst.