We have been studying on the development of new asymmetric two-center catalysis using rare earth alkoxides, and bifunctional sugar and related ligands. As a result, we have found dynamic structural change of chiral rare earth complexes, resulting in the functional change of complexes. The representative examples are shown below. After extensive investigation, the catalyst 3 was found to show higher reactivity than 1 in desymmetrization of meso-aziridines with TMSCN to give b-cyanoamides with better ees. Much to our surprise, the absolute configuration of the products obtained by 1 or 3 was opposite. In addition to the result mentioned above, cyanosilylation of ketones, Strecker reaction of ketoimines, Michael addition and aziridine opening reactions with TMSN₃ will be discussed.