Copper-Mediated Synthesis of (Diethylphosphono) difluoromethyl Thioethers from Diazonium Salts, NaSCN, and TMS-CF2PO(OEt)2

An expedient one-pot synthesis of (diethylphosphono) difluoromethyl thioethers is described consisting of a Sandmeyer thiocyanation with in situ-fluoroalkylation using TMS-CF2PO(OEt)(2) as the fluorine source. Both steps are mediated by copper(I) thiocyanate. The reaction is applicable to a wide range of functional groups, as demonstrated by 22 examples.