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

Abstract 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/ t BuOK combination could construct powerful photoactive architectures to promote single electron transfer for C aryl −F bond reduction via forming highly reducing NHC radical anion. Notably, the strategy was also successful to reduce C aryl −O, C aryl −N, and C aryl −S bonds for biaryl cross‐couplings.