On the origins of stereoselectivity in the aminocatalytic remote alkylation of 5-alkylfurfurals

Abstract

In the manuscript, computational studies on the remote alkylation of 5-alkylfurfurals proceeding via formation of the corresponding trienamine intermediate are presented. By the means of density functional theory (DFT) calculations and the symmetry-adapted perturbation theory (SAPT) method, interesting insights into the mechanism of the reaction have been provided explaining the influence and contribution of different molecular interactions on the observed reactivity as well as on the enantio- and diastereoselectivity of the process. The studies have been extended to the thiophene analogue of the starting furfural derivative and the results obtained verified experimentally.