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

Abstract

AbstractA 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 CF3SII‐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.