Accommodating Styrenes and Unactivated Olefins: Hydrotrifluoromethylation Using O,O'-Dimethyldithiophosphoric Acid as SET Reductant and H Atom Donor.

Styrenes are challenging substrates for current trifluoromethyl radical-involved hydrotrifluoromethylation reactions due to competitive side reactions. Moreover, metal-free hydrotrifluoromethylation of olefins that can simultaneously be compatible with styrenes and unactivated aliphatic alkenes is scarce at present. Herein, we describe an air insensitive, mild, and broadly applicable metal-free hydrotrifluoromethylation protocol by using an appropriate redox system comprising chloro(phenyl)trifluoromethyl-λ3-iodane and presynthesized O,O'-dimethyldithiophosphoric acid (from P2S5 and methanol) for addressing these challenging issues.