The elusive nature of noncovalent π-interactions leads to their infrequent use as a design element in challenging chemical reactions. Stereocontrolling models based on coordinated noncovalent π-interactions were used for the asymmetric dihydroxylation of 1,1-disubstituted aliphatic alkenes. By introduction of a substituted phthalazine ring into the alkene substrates, the enantioselectivity reached 99% under the catalysis of bis-cinchona alkaloid ligands. Density functional theory calculations indicated a well-orchestrated, π-π interaction-directed "sandwich-like" transition state.