Acylation of primary polyfluoroalkanethioamides

► A facile preparation of new NH-acyl derivatives of polyfluoroalkanethioamides. ► Trifluoromethyl-substituted 1,3-dithiethanes were obtained. ► NH-acyl polyfluoroalkanethioamides readily reacted with 2,3-dimethylbutadiene.