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

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