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.

Base-Promoted Annulative Difluoromethylenation of Enaminones with BrCF2CO2Et toward 2,2-Difluorinated 2,3-Dihydrofurans.

A practical method for the synthesis of 2,2-difluorinated 2,3-dihydrofurans has been established via the [4 + 1] annulation of enaminones and BrCF2CO2Et with Na2CO3 promotion. This new protocol does not employ any transition metal reagent and enables the annulative difluoromethylation by the partial cleavage of the C═C double bond. In addition, the further treatment with hydrochloric acid in one pot leads to ß-keto enoic acids (4-oxo-2-butenoic acids) via a formal enaminone C-N carboxylation.