Enantioselective Synthesis of γ-Butyrolactones Bearing γ-Quaternary Stereocenters via Nickel-Catalyzed Reductive Coupling of Acrylates with Ketones.

γ-Butyrolactones with γ-quaternary stereocenters are essential structural components in numerous natural products with significant biological activities. While chiral organocatalysis has seen considerable advancements, the development of intermolecular strategies using transition-metal catalysis has remained limited. Here, we describe a nickel-catalyzed, enantioselective reductive coupling strategy to synthesize chiral γ-butyrolactones by reacting acrylates with ketones. This method employs a chiral quinoline-oxazoline ligand and uses benzyl alcohol as a reductant, achieving high enantioselectivity under mild conditions. Additionally, preliminary mechanistic studies elucidate the reaction pathway.