The intramolecular addition of beta-ketoesters to unactivated alkynes under neutral conditions and at room temperature is described. The method employs triphenylphosphinegold(I) cation as a catalyst for the formation of exo-methylenecycloalkanes. Both monocyclic and bicyclic cyclopentanes and cyclohexanes can be formed in excellent yields and with good diastereoselectivity.