Sodium S -(difluoromethyl) Sulfurothioate: A Readily Available (Deuterio)difluoromethylthiolating Reagent with SCF ₂ H ⁺ , SCF ₂ H – , and SCF ₂ H • Reactivity

In the field of functional small-molecule chemistry, fluorinated small molecules are frequently employed. Difluoromethylthiolated compounds are of particular interest due to their distinctive physiochemical characteristics. We present here the synthesis and application of sodium S-(difluoromethyl) sulfurothioate (NaSO₃SCF₂H) as a potent and adaptable difluoromethylthiolating reagent, which is readily synthesized in a simple step from BnSCF₂H and sodium metabisulfite. Based on experimental and theoretical findings, we demonstrate the utility of NaSO₃SCF₂H in electrophilic, nucleophilic, and radical difluoromethylthiolation reactions, thereby showcasing its unprecedented versatility. Furthermore, the methodology has been expanded to various deuteriodifluoromethylthiolation reactions using NaSO₃SCF₂D.