Citation: Yu Xiong, Li-Jun Hu, Jian-Guo Song, Di Zhang, Yi-Shuang Peng, Xiao-Jun Huang, Jian Hong, Bin Zhu, Wen-Cai Ye, Ying Wang. Structure elucidation of plumerubradins A–C: Correlations between ¹H NMR signal patterns and structural information of [2+2]-type cyclobutane derivatives[J]. Chinese Chemical Letters, ;2025, 36(5): 110149. doi: 10.1016/j.cclet.2024.110149 shu

Structure elucidation of plumerubradins A–C: Correlations between ¹H NMR signal patterns and structural information of [2+2]-type cyclobutane derivatives

Yu Xiong ^{a, b, c, 1} ,
Li-Jun Hu ^{a, b, c, 1} ,
Jian-Guo Song ^{a, b, c} ,
Di Zhang ^a ,
Yi-Shuang Peng ^{a, b, c} ,
Xiao-Jun Huang ^{a, b, c} ,
Jian Hong ^a ,
Bin Zhu ^{d, e, f, *,} ,
Wen-Cai Ye ^{a, b, c, *,} ,
Ying Wang ^{a, b, c, *,}

a.
State Key Laboratory of Bioactive Molecules and Druggability Assessment, Jinan University, Guangzhou 510632, China
b.
Guangdong Province Key Laboratory of Pharmacodynamic Constituents of TCM & New Drugs Research, Guangdong-Hong Kong-Macau Joint Laboratory for Pharmacodynamic Constituents of TCM and New Drugs Research, Jinan University, Guangzhou 510632, China
c.
Center for Bioactive Natural Molecules and Innovative Drugs Research, College of Pharmacy, Jinan University, Guangzhou 510632, China
d.
State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, Shanghai 200237, China
e.
Engineering Research Centre of Pharmaceutical Process Chemistry, Ministry of Education, East China University of Science and Technology, Shanghai 200237, China
f.
Laboratory of Pharmaceutical Crystal Engineering & Technology, East China University of Science and Technology, Shanghai 200237, China

zhubin@ecust.edu.cn

chywc@aliyun.com

wangying_cpu@163.com

Received Date: 20 May 2024
Revised Date: 19 June 2024
Accepted Date: 20 June 2024
Available Online: 21 June 2024

Figures(5)

[2+2]-Type cyclobutane derivatives comprise a large family of natural products with diverse molecular architectures. However, the structure elucidation of the cyclobutane ring, including its connection mode and stereochemistry, presents a significant challenge. Plumerubradins A–C (1–3), three novel iridoid glycoside [2+2] dimers featuring a highly functionalized cyclobutane core and multiple stereogenic centers, were isolated from the flowers of Plumeria rubra. Through biomimetic semisynthesis and chemical degradation of compounds 1–3, synthesis of phenylpropanoid-derived [2+2] dimers 7–10, combined with extensive spectroscopic analysis, single-crystal X-ray crystallography, and microcrystal electron diffraction experiments, the structures with absolute configurations of 1–3 were unequivocally elucidated. Furthermore, quantum mechanics-based ¹H NMR iterative full spin analysis successfully established the correlations between the signal patterns of cyclobutane protons and the structural information of the cyclobutane ring in phenylpropanoid-derived [2+2] dimers, providing a diagnostic tool for the rapid structural elucidation of [2+2]-type cyclobutane derivatives.
- Plumeria rubra,
- Cyclobutane,
- Biomimetic semisynthesis,
- MicroED,
- QM-HiFSA,
- Empirical rule for structure elucidation
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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

Structure elucidation of plumerubradins A–C: Correlations between 1H NMR signal patterns and structural information of [2+2]-type cyclobutane derivatives

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通讯作者: 陈斌, bchen63@163.com

Structure elucidation of plumerubradins A–C: Correlations between ¹H NMR signal patterns and structural information of [2+2]-type cyclobutane derivatives