Chemo-divergent and regioselective branched cross-hydroalkenylation of electron-deficient olefins and vinylarenes directed by (NHC)Ni(II) catalysts.

Catalytic methods for synthesizing highly substituted olefins are crucial for fine chemical and polymer production, yet alkene insertion systems featuring two highly competitive directing effects often scramble the outcome, and strategies to distinguish these effects remain underdeveloped. Here, we present a straightforward chemodivergent and regioselective cross-hydroalkenylation of acrylates and vinylarenes, enabling intermolecular access to distinct conjugated olefin isomers that were previously inaccessible from those abundant substrate classes directly. Our investigations reveal that divergence arises from two sequential, redox-neutral insertion steps, which overcome intrinsic boundaries imposed by a common olefin intermediate formation, oxidative addition, or isomerization. Unlike tactics that rely on varying prefunctionalized substrate pairs, our (NHC)Ni(II)-directed method exploits catalyst-controlled responses to polarized olefin hydrometallation and carbometallation. The green synthesis has instant utility in drug synthesis and in the preparation of electron-deficient, branched allylic centers with up to 97% e.e. This strategy also extends to vinylBpin and vinylsiloxanes, significantly expanding the scope of divergent olefin synthesis.