BINAP‐Accelerated Photoinduced Trifluoromethylation of (Hetero)Aryl Iodides

Abstract Trifluoromethyl groups hold significance in the bioactivity and physical properties of organic molecules. Contemporary approaches to trifluoromethylated aromatics typically involve the coupling of CuCF 3 reagents with aryl halides, which is limited by the difficulty of oxidative addition of copper to organohalides. Herein, a photoinduced ligand‐catalyzed trifluoromethylation/pentafluoroethylation of (hetero)aryl iodides is presented. The conversion of a C─I bond into a C─CF 3 bond is enabled by the photochemistry of copper, which produces aryl radicals with in situ generated CuCF 3 from Ruppert–Prakash reagent under visible light. This radical approach circumvents the challenge of oxidative addition of copper to aryl halides, and a catalytic amount of rac ‐BINAP substantially accelerates the whole process, allowing the reaction to complete within 1 h under very mild conditions without using any additional photo‐redox catalysts. The readily availability of starting material, high efficiency, and broad utility make this transformation attractive for practitioners of synthetic and medicinal chemistry.