In this work, we have demonstrated the synthetic utility of metallic copper-catalyzed C-C coupling reaction involving easily accessible alkenyl boronates, commercially available bromodifluoroacetates and a ligand (TMEDA), and an environment-friendly solvent (DMSO). The method was suitable for a wide range of ,-disubstituted and many -monosubstituted alkenyl boropinacolates, including saturated carbo-and heterocyclic substrates, as well as compounds with additional functional groups and provided a variety of corresponding gem-diflurinated allylacetatesvaluable polyfunctional intermediates for synthetic and medicinal chemistry. On the contrary, -substitution, as well as (hetero)aromatic groups at the  position were typically not tolerated by the developed protocol. In most cases, the process was characterized by low diastereoselectivity, and ca. 1:1 E/Z isomeric mixtures were obtained from pure E or Z alkenyl boronates. The synthetic utility of the proposed method was additionally confirmed by its scale up (to 76 g), as well as some standard functional group transformations at the ester moiety and the double bond. Based on the reaction optimization results, additional mechanistic experiments, and previously reported data, a plausible mechanism of the transformation was disclosed involving the formation of radical and organocopper intermediates.