{Reference Type}: Journal Article
{Title}: DFT investigation of the regioselective allylation of pyrimidine 2'-deoxynucleosides.
{Author}: Gérard H;Lucas-Roper R;Zerrouki R;
{Journal}: Carbohydr Res
{Volume}: 535
{Issue}: 0
{Year}: 2024 Jan 20
{Factor}: 2.975
{DOI}: 10.1016/j.carres.2023.109012
{Abstract}: 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.