Destabilization of Glycosyl Cation by an Electron-Withdrawing Substituent at C-5 Makes Sialylation Reaction More α-Stereoselective
Comparison of the reactivity of sialyl chlorides and bromides based on <i>N</i>-acetylneuraminic acid (Neu5Ac) and its deaminated analogue (KDN) in reactions with MeOH and <i>i</i>-PrOH without a promoter revealed that the acetoxy group at C-5 in a molecule of a sialic acid glycosyl donor can destabilize the corresponding glycosyl cation making the S<sub>N</sub>1-like reaction pathway unfavorable. A change to the S<sub>N</sub>2-like reaction pathway ensures preferential formation of the α-glycoside.
Authors
- Nicolai Vladimirovich Bovin (ORCID: https://orcid.org/0000-0001-8669-4477)
- Alexander Ivanovich Zinin (ORCID: https://orcid.org/0000-0003-1247-939X)
- Alexander Chinarev (ORCID: https://orcid.org/0000-0001-6088-9751)
- Leonid Olegovich Kononov (ORCID: https://orcid.org/0000-0003-1858-7738)
- Zarina Z. Mamirgova (ORCID: https://orcid.org/0000-0002-4294-4718)
- Kirill P. Birin (ORCID: https://orcid.org/0000-0001-6951-2440)
- Alexander O. Chizhov (ORCID: https://orcid.org/0000-0002-4219-8890)
Institutions
- Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Sciences (RU)
- N.D. Zelinsky Institute of Organic Chemistry (RU)
- Institute of Bioorganic Chemistry (RU)
Publication Details
- Journal
- The Journal of Organic Chemistry
- Published
- 2024-12-30
- DOI
- https://doi.org/10.1021/acs.joc.4c02759
- Citations
- 1
- Primary Topic
- Carbohydrate Chemistry and Synthesis
- Type
- article
- Field-Weighted Citation Impact
- 0.25