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

A novel, air and thermally stable, yet highly reactive trifluoromethylthiolating reagent, CF3 SO2 SCF3 (1), was prepared easily in one step from commercially inexpensive CF3 SO2 Na and Tf2 O. 1 is a highly versatile and atom-efficient reagent that can generate one equivalent of CF3 S+ , two equivalents of CF3 S- , or a combination of CF3 S⋅/CF3 ⋅ species. Many high-yielding CF3 S reactions of C, O, S, and N-nucleophiles were achieved, including the simple-step preparations of many reported CF3 S reagents. 1 delivered a hitherto hard-to-synthesize ArOSCF3 that was followed by a novel CF3 SII -rearrangement. Through Cu or TDAE/Ph3 P combinations, 1 generated two equivalents of CF3 S anion species, and the photo-catalyzed reactions of alkenes with 1 provided CF3 /CF3 S-containing products in high atom-efficiency.

Synthesis and Electrophilic Trifluoromethylthiolation Properties of 1-Methyl-4-(trifluoromethylthio)piperazine (MTTP).

A cyclic diamine, 1-methyl-4-(trifluoromethylthio)piperazine (MTTP, 1), prepared by a one-step reaction from commercial materials, is a shelf-stable and powerful electrophilic trifluoromethylthiolating (CF3S) reagent with wide reactivity profile. Activation of 1 with triflic acid (TfOH) yields two reactive species A and B, depending on the molar ratios of TfOH/1. B showed unprecedented high reactivity, making possible the trifluoromethylthiolation of electron-deficient aromatic systems. In addition, B accomplished the trifluoromethylthiolation of active methylene compounds under acidic conditions.