Enantioselective Nickel-Catalyzed Reductive Decarboxylative C(sp3)-C(sp2) Cross-Coupling of Malonic Acid Derivatives

The first enantioselective reductive decarboxylative C(sp3)-C(sp2) cross-coupling of malonic acid derivatives are reported via the intermediacy of redox-active esters (RAEs). A newly modified chiral bis-imidazoline ligand was identified as the optimal ligand to enable this reaction, providing direct access to valuable chiral aryl esters with high efficiency and excellent enantioselectivity. Our protocol is featured by its broad scope and exceptional compatibility with a variety of functional groups, even in the context of late-stage functionalization. In addition, C(sp2)−I could be selectively functionalized with bromo(iodo)arene. The detailed mechanistic studies supported a radical based cross-coupling mechanism.