DFT investigation of the regioselective allylation of pyrimidine 2'-deoxynucleosides.

Autor: Gérard H; Sorbonne Université, CNRS, LCT, UMR 7616, 4 Place Jussieu, Paris, 75005, France., Lucas-Roper R; Univ. Limoges, CNRS, IRCER, UMR 7315, F-87000, Limoges, France. Electronic address: romain.lucas@unilim.fr., Zerrouki R; Univ. Limoges, LABCiS, UR 22722, F-87000, Limoges, France.
Jazyk: angličtina
Zdroj: Carbohydrate research [Carbohydr Res] 2024 Jan; Vol. 535, pp. 109012. Date of Electronic Publication: 2023 Dec 20.
DOI: 10.1016/j.carres.2023.109012
Abstrakt: 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.
Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
(Copyright © 2023 Elsevier Ltd. All rights reserved.)
Databáze: MEDLINE
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