The first highly enantioselective desymmetrization of aziridines with phosphites has been developed. Excellent yields and enantio-selectivities were observed for the reaction with various aziridines using a new class of readily accessible chiral catalysts derived from 9-amino-9-deoxy-epi-cinchonas alkaloids. In studies probing the reaction mechanism, we observed some complexes for the cinchona alkaloid amide-Zn(II) by ESI-MS analysis