Abstract An uncatalyzed three-component reaction employing aliphatic organozinc reagents for the preparation of α-substituted β-ketoesters is described. This modular procedure, which relies on a formal conjugate addition/crossed-Claisen domino reaction between an organozinc, an acrylate and an acyl chloride, allows the straightforward synthesis of the reaction products under mild conditions. The three-component coupling can also be conducted from alkyl iodides, in an even more simple procedure.