DFT calculations and dynamic NMR revealed the coalescent NMR phenomena of the 6/6/6/9 tetracyclic merosesquiterpenoids with an unprecedented 9,15-dioxatetracyclo[8.5.3.04,17.014,18]octadecane core skeleton
Year: 2025
Type: article
Abstract: Two pairs of novel 6/6/6/9 tetracyclic merosesquiterpenoid enantiomers , dauroxonanols A ( 1 ) and B ( 2 ), possessing an unprecedented 9,15-dioxatetracyclo[8.5.3.0 4,17 .0 14,18 ]octadecane core skeleton, were isolated from Rhododendron dauricum . The nuclear magnetic resonance (NMR) spectra of 1 and 2 showed very broad resonances, and 13 C NMR spectrum of 1 exhibited only 13 instead of 22 carbon resonances. These broadening or missing NMR resonances led to a great challenge to elucidate their structures using NMR data analysis. Their structures and absolute configurations of 1 and 2 were finally determined by single crystal X-ray diffraction analysis, chiral separation , and electronic circular dichroism (ECD) calculations. Plausible biosynthetic pathways for 1 and 2 are proposed. Conformational analysis, density functional theory (DFT) calculations, and dynamic NMR assigned the coalescent NMR phenomena of 1 and 2 to the conformational changes of the flexible oxonane ring. Dauroxonanols A ( 1 ) and B ( 2 ) showed potent α-glucosidase inhibitory activities, 2–8 times potent than acarbose , an antidiabetic drug targeting α-glucosidase in clinic.
Source: Chinese Chemical Letters
Authors: Hanqi Zhang, Biao Gao, Yuanyuan Feng, Guijuan Zheng, Zhijun Liu, Lichun Kong, Junjun Liu, Haji Akber Aisa, Guangmin Yao
Language: English
Subfield: Spectroscopy
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
OpenAlex ID: W4409577684