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

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Title: DFT investigation of the regioselective allylation of pyrimidine 2′-deoxynucleosides.
Authors: Gérard, H.1 (AUTHOR), Lucas-Roper, R.1,2 (AUTHOR) romain.lucas@unilim.fr, Zerrouki, R.3 (AUTHOR)
Source: Carbohydrate Research. Jan2024, Vol. 535, pN.PAG-N.PAG. 1p.
Subjects: Pyrimidine nucleosides, Allylation, Pyrimidines, Ion pairs, Nucleoside derivatives, Alkylation, Chelating agents
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. [Display omitted] • A theoretical approach explains the regioselectivity of the alkylation of pyrimidine nucleosides depending on the solvent employed, in terms of kinetics • Reactivity of deprotonated nucleobase was examined using associated and dissociated structures for the Na + -nucleobase ion pair • The increase of the reaction barrier in THF is due to larger Na + binding to the nucleobase • The selected solvent can then modulate the coordination of Na+, favoring the reactivity of one of the different potential nucleophilic sites of the nucleoside [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
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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. [Display omitted] • A theoretical approach explains the regioselectivity of the alkylation of pyrimidine nucleosides depending on the solvent employed, in terms of kinetics • Reactivity of deprotonated nucleobase was examined using associated and dissociated structures for the Na + -nucleobase ion pair • The increase of the reaction barrier in THF is due to larger Na + binding to the nucleobase • The selected solvent can then modulate the coordination of Na+, favoring the reactivity of one of the different potential nucleophilic sites of the nucleoside [ABSTRACT FROM AUTHOR]
ISSN:00086215
DOI:10.1016/j.carres.2023.109012