%0 Journal Article
%T DFT investigation of the regioselective allylation of pyrimidine 2'-deoxynucleosides.
%A Gérard H
%A Lucas-Roper R
%A Zerrouki R
%J Carbohydr Res
%V 535
%N 0
%D 2024 Jan 20
%M 38157586
%F 2.975
%R 10.1016/j.carres.2023.109012
%X To understand the regioselectivity observed in the allylation of pyrimidine nucleosides and to identify the factors directing the reaction, a theoretical study of the regioselective allylation was carried out. Several key points were considered such as: the structure of the deprotonated nucleobase in the presence of Na+; the effect of the solvent on the dissociation and aggregation reactions of thymidine/Na+ ion pair; and the likely allylation reaction mechanisms involved. The results showed that the regioselectivity observed experimentally can be attributed to a greater stability of a dimeric form coupled to an increase of the reaction barrier in THF due to larger Na+ binding to the nucleobase.