AbstractThe first copper‐catalyzed intermolecular enantioselective decarboxylative propargylic alkylation of propargylic esters with β‐keto acids as surrogates of ketones has been successfully developed by using a ketimine P,N,N‐ligand. High yields and excellent enantioselectivities (up to 98% ee) have been achieved under the mild reaction conditions.magnified image