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.