American Chemical Society
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Conformational Properties of Aryl S‑Glucosides in Solution

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journal contribution
posted on 2023-11-07, 08:04 authored by Bhavesh Deore, Ryan W. Kwok, Malika Toregeldiyeva, Jesús T. Vázquez, Mateusz Marianski, Carlos A. Sanhueza
The conformational study of saccharides and glycomimetics in solution is critical for a comprehensive understanding of their interactions with biological receptors and enabling the design of optimized glycomimetics. Here, we report a nuclear magnetic resonance (NMR) study centered on the conformational properties of the hydroxymethyl group and glycosidic bond of four series of aryl S-glucosides. We found that in acetyl-protected and free aryl S-β-glucosides, the rotational equilibrium around the C5–C6 bond (hydroxymethyl group) exhibits a linear dependence on the electronic properties of the aglycone, namely, as the aryl’s substituent electron-withdrawing character increases, the dominance of the gg rotamer declines and the gt contribution rises. Likewise, the conformational equilibrium around the glycosidic C1–S bond also depends on the aglycone’s electronic properties, where glucosides carrying electron-poor aglycones exhibit stiffer glycosidic bonds in comparison to their electron-rich counterparts. In the case of the α anomers, the aglycone’s effect over the glycosidic bond conformation is like that observed on their β isomers; however, we observe no aglycone’s influence over the hydroxymethyl group conformation in the α-glucosides.