Remote Trifluoromethylthiolation Enabled by Organophotocatalytic C–C Bond Cleavage

The first metal-free ring opening/trifluoromethylthiolation of cycloalkanols for the formation of remote C(sp 3 )–SCF 3 bonds has been developed. A variety of trifluoromethylthiolated carbonyl compounds that are otherwise difficult to achieve were prepared in good yields under mild reaction conditions. The reaction is assumed to proceed via C–C bond cleavage of the alkoxyl radical species generated via a photoredox-enabled intramolecular proton-coupled electron transfer process, followed by trifluoromethylthiolation of the resulting C-centered radical with the N -(trifluoromethylthio)phthalimide reagent.