The activation of allylic prop-2-yn-1-ols by the [Ru (μ-O2CH)(CO) 2 (PPh3)] 2 catalyst in the presence of carboxylic acids leads to unsaturated β-ketoesters in one step. The utilization of optically active prop-2-yn-1-ols provides a new stereoselective access to optically active β- ketoesters with retention of configuration at the propargylic carbon.