Chiroptical spectroscopy complemented by quantum chemical calculations accurately predicts the absolute configuration of P-chirogenic compounds

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F25%3A00604459" target="_blank" >RIV/61388963:_____/25:00604459 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/60461373:22310/25:43932277 RIV/60461373:22340/25:43932277

Výsledek na webu

<a href="https://doi.org/10.1016/j.saa.2024.125674" target="_blank" >https://doi.org/10.1016/j.saa.2024.125674</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.saa.2024.125674" target="_blank" >10.1016/j.saa.2024.125674</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Chiroptical spectroscopy complemented by quantum chemical calculations accurately predicts the absolute configuration of P-chirogenic compounds

Popis výsledku v původním jazyce

Model P-chirogenic phosphonates derived from isopinocampheol, offering an excellent experimental system for studying chirality on the phosphorus chiral center, were studied using a set of chiroptical methods including ECD, VCD and ROA. Thanks to their rigidity, limiting the number of possible conformers, we successfully correlated the experimental UV-vis/ECD, IR/VCD and Raman/ROA results with DFT calculations. This allowed us to confidently assign the absolute configuration of our models, and our assignment is consistent with X-ray diffraction (XRD) data. Furthermore, we identified phosphorus-related signals in chiroptical spectra. Specifically, the low frequency P-involving bending modes, which are only visible in ROA spectra and well-reproduced by calculations, may play a key role in determining the stereochemistry of the phosphorus chiral center. These findings lay a solid foundation for further investigation of P-chirogenic compounds, including more complex systems, using chiroptical methods, particularly ROA.

Název v anglickém jazyce

Chiroptical spectroscopy complemented by quantum chemical calculations accurately predicts the absolute configuration of P-chirogenic compounds

Popis výsledku anglicky

Model P-chirogenic phosphonates derived from isopinocampheol, offering an excellent experimental system for studying chirality on the phosphorus chiral center, were studied using a set of chiroptical methods including ECD, VCD and ROA. Thanks to their rigidity, limiting the number of possible conformers, we successfully correlated the experimental UV-vis/ECD, IR/VCD and Raman/ROA results with DFT calculations. This allowed us to confidently assign the absolute configuration of our models, and our assignment is consistent with X-ray diffraction (XRD) data. Furthermore, we identified phosphorus-related signals in chiroptical spectra. Specifically, the low frequency P-involving bending modes, which are only visible in ROA spectra and well-reproduced by calculations, may play a key role in determining the stereochemistry of the phosphorus chiral center. These findings lay a solid foundation for further investigation of P-chirogenic compounds, including more complex systems, using chiroptical methods, particularly ROA.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10406 - Analytical chemistry

Projekt

<a href="/cs/project/GA21-23014S" target="_blank" >GA21-23014S: NMR metodologie pro studium stereochemie bioaktivních molekul obsahujících fosfor</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

Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy

ISSN

1386-1425

e-ISSN

1873-3557

Svazek periodika

330

Číslo periodika v rámci svazku

April

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

9

Strana od-do

125674

Kód UT WoS článku

001399192200001

EID výsledku v databázi Scopus

2-s2.0-85214579844