Deoxygenative conversion of alcohols into difluoromethylthioethers is reported using 2-((difluoromethyl)thio)-3-methylbenzo[d]thiazol-3-ium triflate (BT−SCF2H) as a source of −SCF2H anions. The presence of silver(I) triflate as a catalyst was found to be crucial for stabilizing the in situ-generated anion, while the concomitant formation of a reactive 2-(alkoxy)benzothiazolium electrophile likely ensures a fast onward substitution reaction, avoiding the build-up of −SCF2H. To the best of our knowledge, this process represents the first report of a direct nucleophilic substitution reaction with −SCF2H and delivers products containing the medicinally relevant difluoromethylthio motif in a single step from widely available alcohols
