Redundant 15N-Mediated J-Couplings Reveal an Aglycone Conformation in N-Phenyl Glycosylamines

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F25%3A00641501" target="_blank" >RIV/61388963:_____/25:00641501 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/60461373:22330/25:43932729 RIV/60461373:22340/25:43932729

Výsledek na webu

<a href="https://doi.org/10.1021/acs.joc.5c01892" target="_blank" >https://doi.org/10.1021/acs.joc.5c01892</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.joc.5c01892" target="_blank" >10.1021/acs.joc.5c01892</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Redundant 15N-Mediated J-Couplings Reveal an Aglycone Conformation in N-Phenyl Glycosylamines

Popis výsledku v původním jazyce

Prediction of the conformation of novel N-glycomimetics is a crucial step in their rational design for drug discovery and glycobiology. We investigated the applicability of redundant 15N-mediated J-couplings for predicting the aniline aglycone conformation in 15N-labeled N-phenyl glycosylamines derived from d-glucose (d-Glc), d-mannose (d-Man), d-xylose (d-Xyl), and d-lyxose (d-Lyx). The compounds were prepared directly in an NMR tube by reacting free sugar with 15N-labeled aniline, achieving >90% conversion. The rate of N-phenyl glycosylamine formation depended on the concentration of an open-chain form of the sugar in the solution. In the closed form, the anilino substituent preferred equatorial orientation, which dictated the anomeric ratio and influenced the pyranose ring conformation, particularly in the case of d-Lyx and d-Xyl. The 15N label localized near the conformationally perturbed region provided redundant 15N-mediated J-couplings sensitive to the aniline aglycone conformation. By fitting the density functional theory (DFT)-calculated J-couplings of individual conformers to experimental data, we successfully predicted both the aniline aglycone conformation and the nitrogen atom configuration. Notably, the predicted major conformation of N-phenyl β-d-mannopyranosylamine (6b) corresponded to the conformer observed in the crystal structure.

Název v anglickém jazyce

Redundant 15N-Mediated J-Couplings Reveal an Aglycone Conformation in N-Phenyl Glycosylamines

Popis výsledku anglicky

Prediction of the conformation of novel N-glycomimetics is a crucial step in their rational design for drug discovery and glycobiology. We investigated the applicability of redundant 15N-mediated J-couplings for predicting the aniline aglycone conformation in 15N-labeled N-phenyl glycosylamines derived from d-glucose (d-Glc), d-mannose (d-Man), d-xylose (d-Xyl), and d-lyxose (d-Lyx). The compounds were prepared directly in an NMR tube by reacting free sugar with 15N-labeled aniline, achieving >90% conversion. The rate of N-phenyl glycosylamine formation depended on the concentration of an open-chain form of the sugar in the solution. In the closed form, the anilino substituent preferred equatorial orientation, which dictated the anomeric ratio and influenced the pyranose ring conformation, particularly in the case of d-Lyx and d-Xyl. The 15N label localized near the conformationally perturbed region provided redundant 15N-mediated J-couplings sensitive to the aniline aglycone conformation. By fitting the density functional theory (DFT)-calculated J-couplings of individual conformers to experimental data, we successfully predicted both the aniline aglycone conformation and the nitrogen atom configuration. Notably, the predicted major conformation of N-phenyl β-d-mannopyranosylamine (6b) corresponded to the conformer observed in the crystal structure.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GA22-17586S" target="_blank" >GA22-17586S: 15N izotopické značení v NMR strukturní analýze N-disacharidů</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Organic Chemistry

ISSN

0022-3263

e-ISSN

1520-6904

Svazek periodika

90

Číslo periodika v rámci svazku

45

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

13

Strana od-do

16047-16059

Kód UT WoS článku

001607304700001

EID výsledku v databázi Scopus

2-s2.0-105023181646