Citation: Hanqi Zhang, Biao Gao, Yuanyuan Feng, Guijuan Zheng, Zhijun Liu, Lichun Kong, Junjun Liu, Haji Akber Aisa, Guangmin Yao. DFT calculations and dynamic NMR revealed the coalescent NMR phenomena of the 6/6/6/9 tetracyclic merosesquiterpenoids with an unprecedented 9,15-dioxatetracyclo[8.5.3.0^4,17.0^14,18]octadecane core skeleton[J]. Chinese Chemical Letters, ;2025, 36(9): 111234. doi: 10.1016/j.cclet.2025.111234 shu

DFT calculations and dynamic NMR revealed the coalescent NMR phenomena of the 6/6/6/9 tetracyclic merosesquiterpenoids with an unprecedented 9,15-dioxatetracyclo[8.5.3.0^4,17.0^14,18]octadecane core skeleton

Hanqi Zhang ^{a, 1} ,
Biao Gao ^{a, 1} ,
Yuanyuan Feng ^a ,
Guijuan Zheng ^a ,
Zhijun Liu ^a ,
Lichun Kong ^c ,
Junjun Liu ^a ,
Haji Akber Aisa ^{b, *,} ,
Guangmin Yao ^{a, b, *,}

a.
Hubei Key Laboratory of Natural Medicinal Chemistry and Resource Evaluation, School of Pharmacy, Tongji Medical College, Huazhong University of Science and Technology, Wuhan 430030, China
b.
School of Pharmacy, Xinjiang Medical University, Urumqi 830011, China
c.
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Science, Zhejiang Normal University, Jinhua 321004, China

Received Date: 14 January 2025
Revised Date: 11 April 2025
Accepted Date: 17 April 2025
Available Online: 18 April 2025

Figures(4)

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 ¹³C 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.
- Merosesquiterpenoid enantiomers,
- Rhododendron dauricum,
- Nine-membered ring,
- DFT calculations,
- Dynamic NMR study
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

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

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通讯作者: 陈斌, bchen63@163.com

DFT calculations and dynamic NMR revealed the coalescent NMR phenomena of the 6/6/6/9 tetracyclic merosesquiterpenoids with an unprecedented 9,15-dioxatetracyclo[8.5.3.0^4,17.0^14,18]octadecane core skeleton