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

Abstract A novel, air and thermally stable, yet highly reactive trifluoromethylthiolating reagent, CF 3 SO 2 SCF 3 ( 1 ), was prepared easily in one step from commercially inexpensive CF 3 SO 2 Na and Tf 2 O. 1 is a highly versatile and atom‐efficient reagent that can generate one equivalent of CF 3 S + , two equivalents of CF 3 S − , or a combination of CF 3 S⋅/CF 3 ⋅ species. Many high‐yielding CF 3 S reactions of C , O , S , and N ‐nucleophiles were achieved, including the simple‐step preparations of many reported CF 3 S reagents. 1 delivered a hitherto hard‐to‐synthesize ArOSCF 3 that was followed by a novel CF 3 S II ‐rearrangement. Through Cu or TDAE/Ph 3 P combinations, 1 generated two equivalents of CF 3 S anion species, and the photo‐catalyzed reactions of alkenes with 1 provided CF 3 /CF 3 S‐containing products in high atom‐efficiency.