Synthesis of Difluoromethyl Thioethers from Difluoromethyl Trimethylsilane and Organothiocyanates Generated In Situ

A copper‐CF 2 H complex generated in situ from copper thiocyanate and TMSCF 2 H smoothly converts organothiocyanates into valuable difluoromethyl thioethers. This reaction step can be combined with several thiocyanation methods to one‐pot protocols, allowing late‐stage difluoromethylthiolations of widely available alkyl halides and arenediazonium salts. This strategy enables the introduction of difluoromethylthio groups—a largely unexplored substituent with highly promising properties—into drug‐like molecules.