Stereocontrolled Synthesis and Conformational Analysis of a Series of Disaccharides α,β-<span style="font-variant: small-caps">d</span>-GlcA-(1→3)-α-L-Fuc
<span style="font-variant: small-caps;">D</span>-Glucuronic acid is a fundamental building block of many biologically important polysaccharides, either in its non-substituted form or bearing a variety of substituents, among them sulfates. We have previously performed a study of...
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| Format: | Article |
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MDPI AG
2023-11-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/22/7571 |
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| author | Alexey G. Gerbst Dmitry Z. Vinnitsky Alexandra I. Tokatly Andrey S. Dmitrenok Vadim B. Krylov Nadezhda E. Ustuzhanina Nikolay E. Nifantiev |
| author_facet | Alexey G. Gerbst Dmitry Z. Vinnitsky Alexandra I. Tokatly Andrey S. Dmitrenok Vadim B. Krylov Nadezhda E. Ustuzhanina Nikolay E. Nifantiev |
| author_sort | Alexey G. Gerbst |
| collection | DOAJ |
| description | <span style="font-variant: small-caps;">D</span>-Glucuronic acid is a fundamental building block of many biologically important polysaccharides, either in its non-substituted form or bearing a variety of substituents, among them sulfates. We have previously performed a study of the effects of exhaustive sulfation on the conformational behavior of β-gluronopyranosides. Herein, we report an investigation comparing α- and β-derivatives of this monosaccharide within the title disaccharides using NMR and quantum chemistry approaches. It was found that for α-linked disaccharides, the introduction of sulfates did not greatly affect their conformational behavior. However, for β-derivatives, considerable conformational changes were observed. In general, they resemble those that took place for the monosaccharides, except that NOESY experiments and calculations of intra-ring spin–spin coupling constants suggest the presence of a <sup>1</sup><i>S</i><sub>5</sub> conformer along with <sup>3</sup><i>S</i><sub>1</sub> in the fully sulfated disaccharide. During the synthesis of model compounds, hydrogen bond-mediated aglycone delivery was used as an α-directing stereocontrol approach in the glucuronidation reaction. |
| first_indexed | 2024-03-09T16:34:32Z |
| format | Article |
| id | doaj.art-a7d4fabed246403c910656e45019c0ba |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T16:34:32Z |
| publishDate | 2023-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-a7d4fabed246403c910656e45019c0ba2023-11-24T14:58:17ZengMDPI AGMolecules1420-30492023-11-012822757110.3390/molecules28227571Stereocontrolled Synthesis and Conformational Analysis of a Series of Disaccharides α,β-<span style="font-variant: small-caps">d</span>-GlcA-(1→3)-α-L-FucAlexey G. Gerbst0Dmitry Z. Vinnitsky1Alexandra I. Tokatly2Andrey S. Dmitrenok3Vadim B. Krylov4Nadezhda E. Ustuzhanina5Nikolay E. Nifantiev6Laboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, Moscow 119991, RussiaLaboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, Moscow 119991, RussiaLaboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, Moscow 119991, RussiaLaboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, Moscow 119991, RussiaLaboratory of Synthetic Glycovaccines, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, Moscow 119991, RussiaLaboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, Moscow 119991, RussiaLaboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, Moscow 119991, Russia<span style="font-variant: small-caps;">D</span>-Glucuronic acid is a fundamental building block of many biologically important polysaccharides, either in its non-substituted form or bearing a variety of substituents, among them sulfates. We have previously performed a study of the effects of exhaustive sulfation on the conformational behavior of β-gluronopyranosides. Herein, we report an investigation comparing α- and β-derivatives of this monosaccharide within the title disaccharides using NMR and quantum chemistry approaches. It was found that for α-linked disaccharides, the introduction of sulfates did not greatly affect their conformational behavior. However, for β-derivatives, considerable conformational changes were observed. In general, they resemble those that took place for the monosaccharides, except that NOESY experiments and calculations of intra-ring spin–spin coupling constants suggest the presence of a <sup>1</sup><i>S</i><sub>5</sub> conformer along with <sup>3</sup><i>S</i><sub>1</sub> in the fully sulfated disaccharide. During the synthesis of model compounds, hydrogen bond-mediated aglycone delivery was used as an α-directing stereocontrol approach in the glucuronidation reaction.https://www.mdpi.com/1420-3049/28/22/7571glucuronic acidconformational studiesDFTquantum chemistrystereocontrolglycosylation |
| spellingShingle | Alexey G. Gerbst Dmitry Z. Vinnitsky Alexandra I. Tokatly Andrey S. Dmitrenok Vadim B. Krylov Nadezhda E. Ustuzhanina Nikolay E. Nifantiev Stereocontrolled Synthesis and Conformational Analysis of a Series of Disaccharides α,β-<span style="font-variant: small-caps">d</span>-GlcA-(1→3)-α-L-Fuc Molecules glucuronic acid conformational studies DFT quantum chemistry stereocontrol glycosylation |
| title | Stereocontrolled Synthesis and Conformational Analysis of a Series of Disaccharides α,β-<span style="font-variant: small-caps">d</span>-GlcA-(1→3)-α-L-Fuc |
| title_full | Stereocontrolled Synthesis and Conformational Analysis of a Series of Disaccharides α,β-<span style="font-variant: small-caps">d</span>-GlcA-(1→3)-α-L-Fuc |
| title_fullStr | Stereocontrolled Synthesis and Conformational Analysis of a Series of Disaccharides α,β-<span style="font-variant: small-caps">d</span>-GlcA-(1→3)-α-L-Fuc |
| title_full_unstemmed | Stereocontrolled Synthesis and Conformational Analysis of a Series of Disaccharides α,β-<span style="font-variant: small-caps">d</span>-GlcA-(1→3)-α-L-Fuc |
| title_short | Stereocontrolled Synthesis and Conformational Analysis of a Series of Disaccharides α,β-<span style="font-variant: small-caps">d</span>-GlcA-(1→3)-α-L-Fuc |
| title_sort | stereocontrolled synthesis and conformational analysis of a series of disaccharides α β span style font variant small caps d span glca 1 3 α l fuc |
| topic | glucuronic acid conformational studies DFT quantum chemistry stereocontrol glycosylation |
| url | https://www.mdpi.com/1420-3049/28/22/7571 |
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