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. |
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| 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] |
| Copyright of Carbohydrate Research is the property of Elsevier B.V. and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
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| Header | DbId: egs DbLabel: Engineering Source An: 174708683 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: DFT investigation of the regioselective allylation of pyrimidine 2′-deoxynucleosides. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Gérard%2C+H%2E%22">Gérard, H.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Lucas-Roper%2C+R%2E%22">Lucas-Roper, R.</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<i> romain.lucas@unilim.fr</i><br /><searchLink fieldCode="AR" term="%22Zerrouki%2C+R%2E%22">Zerrouki, R.</searchLink><relatesTo>3</relatesTo> (AUTHOR) – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Carbohydrate+Research%22">Carbohydrate Research</searchLink>. Jan2024, Vol. 535, pN.PAG-N.PAG. 1p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Pyrimidine+nucleosides%22">Pyrimidine nucleosides</searchLink><br /><searchLink fieldCode="DE" term="%22Allylation%22">Allylation</searchLink><br /><searchLink fieldCode="DE" term="%22Pyrimidines%22">Pyrimidines</searchLink><br /><searchLink fieldCode="DE" term="%22Ion+pairs%22">Ion pairs</searchLink><br /><searchLink fieldCode="DE" term="%22Nucleoside+derivatives%22">Nucleoside derivatives</searchLink><br /><searchLink fieldCode="DE" term="%22Alkylation%22">Alkylation</searchLink><br /><searchLink fieldCode="DE" term="%22Chelating+agents%22">Chelating agents</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: 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] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Carbohydrate Research is the property of Elsevier B.V. and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1016/j.carres.2023.109012 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 1 StartPage: N.PAG Subjects: – SubjectFull: Pyrimidine nucleosides Type: general – SubjectFull: Allylation Type: general – SubjectFull: Pyrimidines Type: general – SubjectFull: Ion pairs Type: general – SubjectFull: Nucleoside derivatives Type: general – SubjectFull: Alkylation Type: general – SubjectFull: Chelating agents Type: general Titles: – TitleFull: DFT investigation of the regioselective allylation of pyrimidine 2′-deoxynucleosides. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Gérard, H. – PersonEntity: Name: NameFull: Lucas-Roper, R. – PersonEntity: Name: NameFull: Zerrouki, R. IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 01 Text: Jan2024 Type: published Y: 2024 Identifiers: – Type: issn-print Value: 00086215 Numbering: – Type: volume Value: 535 Titles: – TitleFull: Carbohydrate Research Type: main |
| ResultId | 1 |
