Transition-Metal-Free C-H Trifluoromethylthiolation of N,N -Disubstituted Enaminones To Access CF 3 S-Functionalized Enaminones and Their Application in the Synthesis of CF 3 S-Heteroaryls.

The α-C-H trifluoromethylthiolation of N,N -disubstituted enaminones has been achieved with simple and cheap CF 3 SO 2 Na as the CF 3 S source. The reactions were run at mild temperature (0 °C to rt) using POCl 3 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 CF 3 S-functionalized enaminones have been proven as useful building blocks in the synthesis of various CF 3 S-functionalized heteroaromatic compounds by simple annulation reactions.