Abstract: | An enantioselective 1,4‐addition of α,β‐unsaturated carboxylic acids with cycloalkanones has been developed by using chiral amine–boronic acid cooperative catalysts. In the presence of a chiral amine and boronic acid, cycloalkanones and carboxylic acids are activated as chiral enamines and mixed anhydrides, respectively. The corresponding 1,4‐adducts are obtained in high yield with high enantioselectivity. Furthermore, subsequent oxylactonization of the 1,4‐adducts gives spirolactones with high diastereoselectivity. |