Nickel-Catalyzed Asymmetric Carboacylation of Alkenes via CO Transfer.

We report a nickel-catalyzed asymmetric carboacylation of alkenes using acyl chlorides as bifunctional carbon and carbonyl sources. The reaction proceeds via a functional group transfer mechanism, enabling efficient access to enantioenriched ketones without the use of toxic CO gas. Precise control of CO extrusion and reinsertion affords broad substrate scope and high enantioselectivity, with good tolerance of functional groups commonly found in drug-like molecules. Mechanistic studies, including radical inhibition experiments, isotopic labeling, and DFT calculations, support a Ni0/NiII/NiIII/NiI catalytic cycle involving reversible CO transfer and stereocontrolled migratory insertion.