Caiwen Wan, Changtong Shao, Ruolan Leng, Rui Yang, Dingfeng Yang, Jie Gao, Yixi Bao, Yuanxue Yi, Yuanyuan Li
We report an autoinductive, visible-light-mediated ( E )-β-trifluoromethylation of enamides using sodium trifluoromethanesulfinate. This protocol eliminates exogenous catalysts by leveraging an in situ generated pentacoordinate sulfur(VI) species as the photosensitizer. Characterized by mild conditions and broad substrate compatibility, the method exhibits promising scalability, as evidenced by a gram-scale continuous-flow synthesis. This oxidant- and catalyst-free strategy provides a robust, scalable paradigm for accessing valuable trifluoromethylated building blocks.