Visible‐Light‐Induced N‐Heterocyclic Carbene‐Catalyzed Single Electron Reduction of Mono‐Fluoroarenes

Fluoroarenes are abundant and readily available feedstocks. However, due to the high reduction potentials of mono-fluoroarenes, their photoreduction remains a continuing challenge, motivating the development of efficient activation modes to address this issue. This report presents the blue light-induced N-heterocyclic carbene (NHC)-catalyzed single electron reduction of mono-fluoroarenes for biaryl cross-couplings. We discovered that under blue light irradiation, NHC/tBuOK combination could construct powerful photoactive architectures to promote single electron transfer for Caryl–F bond reduction via forming highly reducing NHC radical anion. Notably, the strategy was also successful to reduce Caryl–O, Caryl–N, and Caryl–S bonds for biaryl cross-couplings.