Preparation and Reactivity Study of a Versatile Trifluoromethylthiolating Agent: S-Trifluoromethyl Trifluoromethanesulfonothioate (TTST)

A novel, air and thermally stable, yet highly reactive trifluoromethylthiolating reagent, CF₃SO₂SCF₃ ( 1 ), was prepared easily in one step from commercially inexpensive CF₃SO₂Na and Tf₂O. 1 is a highly versatile and atom-efficient reagent that can generate one equivalent of CF₃S ⁺ , two equivalents of CF₃S⁻, or a combination of CF₃S⋅/CF₃⋅ species. Many high-yielding CF₃S reactions of C, O, S, and N-nucleophiles were achieved, including the simple-step preparations of many reported CF₃S reagents. 1 delivered a hitherto hard-to-synthesize ArOSCF₃ that was followed by a novel CF₃S^II-rearrangement. Through Cu or TDAE/Ph₃P combinations, 1 generated two equivalents of CF₃S anion species, and the photo-catalyzed reactions of alkenes with 1 provided CF₃/CF₃S-containing products in high atom-efficiency.