The first highly enantioselective organocatalytic reaction employing 2-hydroxyacetophenones is disclosed, namely Michael-hemiacetalization reaction of 2-hydroxyacetophenones with enals. The combination of a primary amine and a secondary amine catalyst was found to be the best choice for this methodology. The products of this reaction were obtained in high enantio- and diastereoselectivities and were converted to a variety of biologically important γ-butyrolactones.