title: High level ab initio exploration on the conversion of carbon dioxide into oxazolidinones: the mechanism and regioselectivity.
abstract: Density functional theory (DFT) and second order Møller-Plesset perturbation (MP2) calculations, employing the 6-311++G(d,p) basis set, were carried out on alkyl-substituted aziridines to explore the reaction mechanisms and regioselectivity associated with their ring-opening conversions to oxazolidinones, in the presence of carbon dioxide. Computational results, employing the self-consistent reaction field polarizable continuum model (SCRF(PCM/Bader)), indicated that the conversions proceed with thermodynamic ease in THF solvent at room temperature. It is proposed that the N-alkylaziridine promotes ring opening through a SN2 attack of the iodide ion, of catalytic lithium iodide, on the preformed complex. The oxazolidinone regioisomer ratio is highly sensitive to aziridine ring-carbon substitution. Therein, monophenyl substitutions show preference to opening more highly substituted carbon-nitrogen bonds, providing rationale as to why experimental works result in an exclusive oxazolidinone regioisomer product.
authors.affiliation: College of Chemistry, Beijing Normal University, Beijing 100875, PR of China.
authors.forename: Wei-Hua
authors.initials: WH
authors.lastname: Mu
authors.forename: Gregory A
authors.initials: GA
authors.lastname: Chasse
authors.forename: De-Cai
authors.initials: DC
authors.lastname: Fang