Destabilization of Glycosyl Cation by an Electron-Withdrawing Substituent at C-5 Makes Sialylation Reaction More α-Stereoselective

Destabilization of Glycosyl Cation by an Electron-Withdrawing Substituent at C-5 Makes Sialylation Reaction More α-Stereoselective Full article

Journal

Journal of Organic Chemistry
ISSN: 1520-6904 , E-ISSN: 0022-3263

Output data

Year: 2025, Volume: 90, Number: 1, Pages: 931-937 Pages count : 7 DOI: 10.1021/acs.joc.4c02759

Authors

Mamirgova Zarina Z. ¹ , Zinin Alexander I. ¹ , Chinarev Alexander A. ² , Chizhov Alexander O. ¹ , Birin Kirill P. ³ , Bovin Nicolai V. ² , Kononov Leonid O. ¹

Affiliations

1	N.D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, Leninsky prosp. 47, Moscow 119991, Russian Federation
2	M.M. Shemyakin−Yu.A. Ovchinnikov Institute of Bioorganic Chemistry of the Russian Academy of Sciences, Miklukho-Maklaya st. 16/10, Moscow 117997, Russian Federation
3	Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences, Leninsky prosp. 31-4, Moscow 119071, Russian Federation

Comparison of the reactivity of sialyl chlorides and bromides based on N-acetylneuraminic acid (Neu5Ac) and its deaminated analogue (KDN) in reactions with MeOH and 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 SN1-like reaction pathway unfavorable. A change to the SN2-like reaction pathway ensures preferential formation of the α-glycoside.

Mamirgova Z.Z. , Zinin A.I. , Chinarev A.A. , Chizhov A.O. , Birin K.P. , Bovin N.V. , Kononov L.O.
Destabilization of Glycosyl Cation by an Electron-Withdrawing Substituent at C-5 Makes Sialylation Reaction More α-Stereoselective
Journal of Organic Chemistry. 2025. V.90. N1. P.931-937. DOI: 10.1021/acs.joc.4c02759 WOS OpenAlex

Web of science:	WOS:001387017400001
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