文献类型：期刊文献

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

作者：Xiong, Yu[1,2,3];Hu, Li-Jun[1,2,3];Song, Jian-Guo[1,2,3];Zhang, Di[1];Peng, Yi-Shuang[1,2,3];Huang, Xiao-Jun[1,2,3];Hong, Jian[1];Zhu, Bin[4,5,6];Ye, Wen-Cai[1,2,3];Wang, Ying[1,2,3]

机构：[1]Jinan Univ, State Key Lab Bioact Mol & Druggabil Assessment, Guangzhou 510632, Peoples R China;[2]Jinan Univ, Guangdong Prov Key Lab Pharmacodynam Constituents, Guangdong Hong Kong Macau Joint Lab Pharmacodynam, Guangzhou 510632, Peoples R China;[3]Jinan Univ, Coll Pharm, Ctr Bioact Nat Mol & Innovat Drugs Res, Guangzhou 510632, Peoples R China;[4]East China Univ Sci & Technol, State Key Lab Bioreactor Engn, Shanghai 200237, Peoples R China;[5]East China Univ Sci & Technol, Engn Res Ctr Pharmaceut Proc Chem, Minist Educ, Shanghai 200237, Peoples R China;[6]East China Univ Sci & Technol, Lab Pharmaceut Crystal Engn & Technol, Shanghai 200237, Peoples R China

年份：2025

卷号：36

期号：5

外文期刊名：CHINESE CHEMICAL LETTERS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001449316300001)】；

基金：This work was financially supported by the National Key R&D Program of China (No. 2023YFC3503902) , the National Nat-ural Science Foundation of China (Nos. 822936 81 (822936 80) and 82321004) , the Guangdong Basic and Applied Basic Research Foundation (Nos. 2022B1515120015 and 2021A1515111021) , the Guangdong Major Project of Basic and Applied Basic Research (No. 2023B03030 0 0 026) , and the Science and Technology Projects in Guangzhou (No. 202102070 0 01) . The authors are grateful to Mr. Matthias Niemitz, the founder of NMR Solutions Ltd., for granting access to Cosmic Truth software.

语种：英文

外文关键词：Plumeria rubra; Cyclobutane; Biomimetic semisynthesis; MicroED; QM-HiFSA; Empirical rule for structure elucidation

摘要：[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 1 H 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. (c) 2025 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.