Chemo‐ and Enantioselective Nickel‐Catalyzed Alkenylative Coupling of Alkynes and Aldehydes or Ketones for the Facile Synthesis of 1,3‐Dienols

A nickel‐catalyzed alkenylative coupling of aldehydes(ketones), alkynes, and alkenyl boronic acids is reported, providing a modular and efficient route to stereodefined 1,3‐dienols from readily available substrates. This transformation exploits the controlled reactivity of oxanickelacycle intermediates and avoids the use of nucleophilic or moisture‐sensitive dienyl organometallic reagents. Broad substrate scope is observed for all three components, delivering multisubstituted dienols with high regioselectivity and good to excellent yields. An enantioselective variant employing a P ‐chiral monophosphine ligand furnishes chiral dienols with good enantiocontrol (up to 99% ee). In addition, an intramolecular version with 1,6/1,7‐ynones enables the asymmetric synthesis of tertiary alcohols bearing exocyclic dienes. This work significantly expands the synthetic toolkit for dienol synthesis and showcases the versatile reactivity of oxanickelacycle intermediates in multicomponent coupling.