Transition-Metal-Free C–H Trifluoromethylthiolation of N,N-Disubstituted Enaminones To Access CF₃S-Functionalized Enaminones and Their Application in the Synthesis of CF₃S-Heteroaryls

The α-C–H trifluoromethylthiolation of N,N-disubstituted enaminones has been achieved with simple and cheap CF3SO2Na as the CF3S source. The reactions were run at mild temperature (0 °C to rt) using POCl3 as the only reducing reagent. The work represents the first example on the synthesis of α-trifluoromethylthio enaminones via direct C–H functionalization. In addition, the resulting CF3S-functionalized enaminones have been proven as useful building blocks in the synthesis of various CF3S-functionalized heteroaromatic compounds by simple annulation reactions.