Transition-metal-free trifluoromethylthiolation and difluoromethylthiolation of thiols with trifluoromethanesulfonyl chloride and difluoromethanesulfonyl chloride

Triphenylphosphine-mediated metal-free trifluoromethylthiolation and difluoromethylthiolation of thiols by CF₃SO₂Cl and CHF₂SO₂Cl to synthesize trifluoromethyl disulfides and difluoromethyl disulfides, respectively, was achieved at room temperature. Iodine generated in situ from iodide facilitated this reaction via the formation of iodotriphenylphosphonium iodide which could serve as a reducing agent in this transformation. Readily available reagents and mild reaction conditions without transition-metals allow this protocol to be more practical than traditional methods.