The features of asymmetric Ni(II)-catalyzed Michael addition of 1,3-dicarbonyl compounds to nitroolefins has been investigated by DFT and experimental studies. The results support a mechanistic pathway that proceeds via formation of enolate, intramolecular nucleophilic attack on coordinated nitroolefin and protonation of resulting nitronate complex. The calculated difference in activation energies for the formation of enantiomeric Michael adducts in the case of diethyl malonate and ω-nitrostyrene are remarkably close to the experimental values, obtained from enantioselectivity-temperature dependence. The presence of H-bond in the ω-nitrostyrene complex induced further investigation of the reaction path of cinnamic aldehyde, thah cannot form such bond. Comparison of the energy profiles for ω-nitrostyrene and cynnamic aldehyde as Michael acceptors shows the important role of hydrogen bond formation between Ni complex and reagent for emergence of enantioselectivity.