Iron‐Catalyzed Regioselective Alkenylboration of Olefins

Abstract The first examples of an iron‐catalyzed three‐component synthesis of homoallylic boronates from regioselective union of bis(pinacolato)diboron, an alkenyl halide (bromide, chloride or fluoride), and an olefin are disclosed. Products that bear tertiary or quaternary carbon centers could be generated in up to 87 % yield as single regioisomers with complete retention of the olefin stereochemistry. With cyclopropylidene‐containing substrates, ring cleavage leading to trisubstituted E ‐alkenylboronates were selectively obtained. Mechanistic studies revealed reaction attributes that are distinct from previously reported alkene carboboration pathways.