A modular, stereoselective route to trisubstituted ()-alkenyl (MIDA)boronates is described, consisting of the radical addition-fragmentation of dithiocarbonates to 2-(MIDA)boronyl-3-(2'-fluoro-pyridyl-6'-oxy)-alkenes. The bulky (MIDA)boronate ensures a highly stereoselective fragmentation that is enhanced by the poor stabilization of the radical adjacent to the tetravalent boron atom. The vinyl boronate precursors are prepared from propargyl alcohols by copper-catalyzed regioselective protoboration of their fluoropyridoxy derivatives, with the fluoropyridine acting as an internal directing group.
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