Nickel‐Catalyzed Enantioselective Decarboxylative Acylation: Rapid, Modular Access to α‐Amino Ketones**

A new approach to the enantiocontrolled synthesis of α-amino ketone derivatives is disclosed by employing a decarboxylative acylation strategy. Thus, when an acyl chloride and an α-amido-containing redox-active ester are exposed to a nickel catalyst, chiral ligand, and metal reductant, α-amido ketones are produced in good yield and high ee. The reaction exhibits broad substrate scope, can be easily scaled up, and is applied to dramatically simplify the synthesis of several known structures.