The high importance of fluorinated compounds in medicinal chemistry and beyond implies a constant need for novel Fluorine-containing chemotypes and synthesis thereof. In this area, bromodifluoroacetic acid and its derivatives have been known for a long time as a valuable CF2 unit source applicable to a variety of transformations. To date, the known reactivity of bromodifluoroacetate 1 towards boronic derivatives has been mostly described for aromatic substrates and included Suzuki-type C-C coupling reactions. On the contrary, alkenyl boronates 2 have been known to react with compound 1 via the ATRA pathway providing α-haloboronates of type 3 (Scheme 2, A). In this work, we for the first time demonstrate an alternative reactivity profile for substrates 1 and 2 resulting in ipso-substitution of the boron-containing moiety (Scheme 2, B). The developed protocol employs metallic copper catalysis and provides an easy access CF2-homologs of acrylates 4valuable organofluorine intermediates for the synthetic and medicinal chemistrystarting from readily available bromodifluoroacetate 1 and alkenyl boropinacolates 2. Scheme 1. Alkenyl boronates as the substrates in: (A) atom transferradical addition (ATRA); (B) radical ipsosubstitution; (C) C-B transmetalative reactions.