A computational study of 2-(chloromethyl)oxirane ring opening by bromide and acetate anions considering electrophilic activation with cations of alkali metals / Kseniia Yutilova, Yuliia Bespal’ko, Elena Shved.

Ring opening of 2-(chloromethyl)oxirane via the nucleophilic substitution with bromide and acetate anions was investigated using density functional theory (DFT) calculations. It was shown that the geometry of the transition states and the activation parameters of the reactions correspond to those of SN2-like mechanism. The nature of localized transition states was analyzed using More O’Ferrall – Jencks plots. The quantum chemical simulations of the potential energy surface for the ring-opening reaction of oxirane by nucleophiles confirmed the theoretical assumptions about the favored path of interactions, which is a backside α-attack of nucleophile. The effect of alkali metal cation (Li+, Na+, K+) on that path was estimated. It was found that the electrophilic activation with alkali metal cation is more pronounced in the reaction of 2-(chloromethyl)oxirane with dissociated ions, than with ionic pairs.