On the origin of the electronic and magnetic circular dichroism of naphthyl C-glycosides: Anomeric configuration

0580580 - ÚOCHB 2025 RIV NL eng J - Journal Article
Choutka, Jan - Parkan, Kamil - Pohl, Radek - Kaminský, Jakub
On the origin of the electronic and magnetic circular dichroism of naphthyl C-glycosides: Anomeric configuration.
Carbohydrate Research. Roč. 535, January (2024), č. článku 109021. ISSN 0008-6215. E-ISSN 1873-426X
R&D Projects: GA MŠMT LTAUSA18085; GA ČR(CZ) GA22-17586S
Research Infrastructure: CESNET II - 90042; CERIT-SC - 90085
Institutional support: RVO:61388963
Keywords : electronic circular dichroism * magnetic circular dichroism * aryl C-glycosides * anomeric configuration * conformations
OECD category: Physical chemistry
Impact factor: 3.1, year: 2022
Method of publishing: Limited access
https://doi.org/10.1016/j.carres.2023.109021

Aryl C-glycosides, in which the glycosidic bond is changed to a carbon-carbon bond, are an important family of biologically-active compounds. They often serve as secondary metabolites or exhibit antibiotic and cytostatic activities. Their stability to hydrolysis has made them attractive targets for new drugs. Their conformational behavior often strongly influences the resulting function. Their detailed structural and conformational description is thus highly desirable. This work studies the structure of three different naphthyl C-glycosides using UV-vis absorption as well as electronic and magnetic circular dichroism. It also describes their conformational preferences using a combination of molecular dynamics and DFT calculations. The reliability of these preferences has been verified by simulations of spectral properties and a comparison with their measured spectra. In particular, ECD spectroscopy has been shown to distinguish easily between alpha- and beta-pseudoanomers of aryl C-glycosides. Computer simulations and spectral decomposition have revealed how the resulting ECD patterns of the naphthyl glycosides studied are influenced by different conformer populations. In conclusion, reliable ECD patterns cannot be calculated by separating the naphthyl rotation from other conformational motions. MCD patterns have been similar for all the naphthyl C-glycosides studied. No clear diagnostic features have been found for either the pseudoanomeric configuration or the preferred hydroxymethyl rotamer. Nevertheless, the work has demonstrated the potential of MCD for the study of aryl glycosides interacting with proteins.
Permanent Link: https://hdl.handle.net/11104/0349343


Research data: OSF