The first highly enantioselective nucleophilic addition reaction of phosphites with 2H-azirines has been developed. The reaction was applied to various 3-substituted 2H-azirines using novel chiral bis(imidazoline)/Zn catalysts to afford products in good yield with high enantioselectivity. The transformation of the obtained optically active aziridines showed that 2H-azirines act as either α,β- or β,β-dicarbocationic amine synthons.

The first catalytic enantioselective reaction of 2H-azirines with thiols has been developed. The obtained aziridines can be converted to optically active oxazolines, aziridylamides, or α-sulfonyl esters. Transformation of these optically active aziridines showed that 2H-azirines act as β,β-dicarbocationic amine synthons.

The first highly enantioselective nucleophilic addition reaction of phosphites with 2H‐azirines has been developed. The reaction was applied to various 3‐substituted 2H‐azirines using novel chiral bis(imidazoline)/ZnII catalysts to afford products in good yield with high enantioselectivity. The transformation of the obtained optically active aziridines showed that 2H‐azirines act as either α,β‐ or β,β‐dicarbocationic amine synthons.