A highly chemo‐, enantio‐, and regioselective synthesis of furanones bearing an α,α‐disubstituted quaternarystereogeniccenter is reported. The Cu‐catalyzedenantioselective conjugate addition of organoaluminum reagents to unsaturated ketoesters at room temperature and subsequent lactonization took place. Synthetic transformations of furanones represent facile approaches to various cyclic or acyclic