Controllable Phosphorothiotrifluoromethylation and Hydrotrifluoromethylation of Unactivated Alkenes in Water

Metal-free redox strategy provides an efficient and simple mode for the difunctionalization of olefins, but is not well used for trifluoromethyl-sufuration mainly because such a process is accompanied by many competitive reactions. Here, we report two selective alkene difunctionalizations, phosphorothiotrifluoromethylation and hydrotrifluoromethylation, by taming a three-component redox reaction under metal-free conditions. The method features greenness, operational simplicity, high efficiency, gram-scale synthesis, and late-stage functionalization, and is also applicable to corresponding perfluoroalkylation-based reactions.