Arenethiolate as a Dual Function Catalyst for Photocatalytic Defluoroalkylation and Hydrodefluorination of Trifluoromethyls

Thiol is known to act as a hydrogen atom transfer catalyst working in synergy with a photocatalyst in photoredox catalysis, but we report herein that an arene thiolate with an appropriate substituent can be photoactivated under visible light to function as both a strongly reducing electron-donating redox catalyst and a HAT catalyst to enable catalytic C–F activation of trifluoromethyl substrates for selective hydrodefluorination and coupling with various alkenes in the presence of formate salts. These reactions demonstrate the promising utility of arenethiolates as dual function photocatalysts. The synthetic utility of this method is demonstrated by the broad scope of amenable trifluoromethyl substrates, including trifluoromethylated (hetero)arenes, trifluoroacetates, and trifluoroacetamides, which exhibited high levels of chemoselectivity. The reaction efficacy allows site-selective late-stage functionalization of multitrifluoromethylated bioactive compounds and pharmaceuticals