Highly enantioselective Michael addition of 1,3-dicarbonyl compounds and nitromethane to 4-oxo-4-arylbutenoates catalyzed by N,N'-dioxide-Sc(OTf)(3) complexes has been developed. Using 0.5-2 mol % catalyst loading, various alpha-stereogenic esters were obtained regioselectively with excellent yields (up to 97 %) and enantioselectivities (up to >99 % ee). Moreover, the reaction performed well under nearly solvent-free conditions. The products with functional groups are ready for further transformation, which showed the potential value of the catalytic approach. According to the experimental results and previous reports, a plausible working model has been proposed to explain the origin of the activation and the asymmetric induction.