Intramolecular ring-opening from a CO 2 -derived nucleophile as the origin of selectivity for 5-substituted oxazolidinone from the (salen)Cr-catalyzed [aziridine + CO 2 ] coupling

] coupling to form oxazolidinone was found to exhibit excellent selectivity for the 5-substituted oxazolidinone product in the absence of any cocatalyst. Quantum mechanical calculations suggest that the preferential opening of the substituted C-N bond of the aziridine over the unsubstituted C-N bond is a key factor for this selectivity, a result that is supported by experiment with several phenyl-substituted aziridines. In the presence of external nucleophile such as dimethyl aminopyridine (DMAP), the reaction changes pathway and the ring-opening process is regulated by the steric demand of the nucleophile.