Sodium <i>S</i> -(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 (NaSO 3 SCF 2 H) as a potent and adaptable difluoromethylthiolating reagent, which is readily synthesized in a simple step from BnSCF 2 H and sodium metabisulfite. Based on experimental and theoretical findings, we demonstrate the utility of NaSO 3 SCF 2 H in electrophilic, nucleophilic, and radical difluoromethylthiolation reactions, thereby showcasing its unprecedented versatility. Furthermore, the methodology has been expanded to various deuteriodifluoromethylthiolation reactions using NaSO 3 SCF 2 D.