The first enantioselective Michael addition of malonates to acyclic β,β-disubstituted enones has been developed. Sterically hindered β-trifluoromethyl α,β-unsaturated 2-acyl thiazoles and benzothiazoles were found to be the most reactive groups of enones in the reaction catalyzed by bifunctional tertiary amine-thioureas (2-5 mol %). However, application of hyperbaric conditions (8-10 kbar) was required. The adducts containing quaternary stereogenic centers with a CF