After many years of neglection in synthetic laboratories, radical chemistry receives growing attention, offering the novel types of chemical reactivities. In particular, radical reactions of alkenyl boronates have been studied in numerous works previously. One of the possible reaction pathways include radical addition with preservation of the boronate moiety (Scheme 1, A). These transformations have been discussed thoroughly in several review articles and typically include atom transferradical addition (ATRA). The process starts with Giese-type radical addition to the double bond providing α-boryl radical. The latter intermediate can get halogen from the reaction media by the halogen atom transfer (XAT) process, with simultaneous propagation of the reaction chain. Alternatively, radical-polar crossover (RPC) reaction can occur at certain conditions with generation of either cationic or anionic intermediates, eventually leading to the formation of the target addition products. In this case, it was demonstrated that 1,2-migration from the boron substituent often plays a crucial role in the overall reaction outcome. Substrates with substituents stabilizing β-boryl radical species (e.g., styryl boronates or alkenyl trifluoroborates) demonstrate an opposite regioselectivity at the radical addition step (Scheme 1, B). The resulting intermediate undergoes one-electron oxidation through a SET mechanism. Next, the carbocation formed readily eliminates boronic species, formally giving the ipso-substitution products. While typical conditions for the above transformations require an exogeneous radical source (e.g., through irradiation), analogous results can be achieved by the use of C-B transmetalation (Scheme 1, C). In this case, the selectivity of the reaction is governed solely by the boronate moiety position rather than by electronic properties of the substrate.