DFT mechanistic study of the chemical fixation of CO by aziridine derivatives.

Using density functional theory (DFT), we treat the reaction of coupling of CO with aziridine in gas phase, in the presence of water and of a green catalyst (NaBr). Computations show that, in gas phase, this ring-opening conversions to oxazolidinones initiates by coordinating a CO molecule to the nitrogen atom of the aziridine. Then, a nucleophilic interaction between one oxygen atom of the coordinated CO and the carbon atom of the aziridine occurs. For methyl substituted aziridine, two pathways are proposed leading either to 4-oxazolidinone or to 5-oxazolidinone. Besides, we show that the activation energy of this reaction reduces in aqueous solution, in the presence of a water molecule explicitly or NaBr catalyst. In addition, the corresponding reaction mechanisms and regioselectivity associated with this ring-opening conversions to oxazolidinones, in the presence of carbon dioxide are found to be influenced by solvent and catalyst. The present findings should allow better designing regioisomer oxazolidinones relevant for organic chemistry, medicinal and pharmacological applications.