Stereoconvergent and Enantioselective Synthesis of <i>Z</i>-Homoallylic Alcohols via Nickel-Catalyzed Reductive Coupling of <i>Z</i>/<i>E</i>-1,3-Dienes with Aldehydes

Stereoconvergent reactions enable the transformation of mixed stereoisomers into well-defined, chiral products─a crucial strategy for handling <i>Z</i>/<i>E</i>-mixed olefins, which are common but challenging substrates in organic synthesis. Herein, we report a stereoconvergent and highly enantioselective method for synthesizing <i>Z</i>-homoallylic alcohols via the nickel-catalyzed reductive coupling of <i>Z</i>/<i>E</i>-mixed 1,3-dienes with aldehydes. This process is enabled by an <i>N</i>-heterocyclic carbene ligand characterized by <i>C</i>₂-symmetric backbone chirality and bulky 2,6-diisopropyl <i>N</i>-aryl substituents. Our method achieves excellent stereocontrol over both enantioselectivity and <i>Z</i>-selectivity in a single step, producing chiral <i>Z</i>-homoallylic alcohols that are valuable in natural products and pharmaceuticals.