Abstract

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 ArSOCF3 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.

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