Rationalizing the Stereoelectronic Influence of Interglycosidic Bond Conformations on the Reactivity of 1,4-O-Linked Disaccharide Donors

Autor:	Cheng-Chung Wang, Welday Desta Weldu
Rok vydání:	2021
Předmět:	Glycan Anomer biology Stereochemistry Organic Chemistry Disaccharide Leaving group Dihedral angle chemistry.chemical_compound chemistry biology.protein Side chain Reactivity (chemistry) Protecting group
Zdroj:	The Journal of Organic Chemistry. 86:17906-17917
ISSN:	1520-6904 0022-3263
DOI:	10.1021/acs.joc.1c02207
Popis:	Disaccharide donors are key precursors in convergent glycan synthesis strategies. Unexpectedly, we observed that disaccharide thioglycosyl donors containing 1,4-O-linked α-glycosidic bonds are much more reactive than their β-analogues with the same protecting group pattern. Herein, we rationalized that such a difference in their reactivity is attributed to the conformation of the 1,4-O-interglycosidic bond which is controlled by anomeric and exo-anomeric effects. Moreover, the conformational preferences of these donors are dictated by the dihedral angles ϕ and ψ of their interglycosidic linkages and the torsional angle ω of their side chain along the C5-C6 bond. This fundamental research clarifies how the long-range stereoelectronic effects from the nonreducing end sugar can influence the reactivity of the leaving group at the reducing end and the behavior of disaccharide donors thereof.
Databáze:	OpenAIRE
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