Tao Guang, Hu Xin-Yue, Liu Hong-Xing, Li Xing-Ren, Shao Li-Dong, Xu Gang
Yunnan Key Laboratory of Southern Medicinal Utilization, School of Chinese Materia Medica, Yunnan University of Chinese Medicine, Kunming, 650500, China.
State Key Laboratory of Phytochemistry and Natural Medicines, and Yunnan Key Laboratory of Natural Medicinal Chemistry, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming, 650201, China.
Nat Prod Bioprospect. 2025 May 13;15(1):32. doi: 10.1007/s13659-025-00517-8.
Two concise and efficient synthetic routes were developed for the synthesis of three 1,7-diarylheptanoids (1-3) containing a 1,4-pentadiene unit, which were originally isolated from Ottelia acuminata var. acuminata. The first approach focused on the construction of linear diarylheptanoids 1 and 3 featuring a (1E,4E)-pentadiene moiety, via a Suzuki coupling reaction. The second strategy enabled the synthesis of sixteen-membered macrocyclic ether 2 with a (1Z,4E)-pentadiene unit. The challenging macrocyclization was successfully accomplished through an Ullmann coupling. Notably, the formation of the Z-olefin within the macrocyclic framework was promoted by the inherent ring strain of diarylether-type heptane system, which preferentially stabilizes this particular configuration.
开发了两种简洁高效的合成路线，用于合成三种含有1,4-戊二烯单元的1,7-二芳基庚烷类化合物（1-3），这些化合物最初是从尖叶水车前中分离得到的。第一种方法侧重于通过铃木耦合反应构建具有（1E,4E）-戊二烯部分的线性二芳基庚烷类化合物1和3。第二种策略实现了具有（1Z,4E）-戊二烯单元的十六元大环醚2的合成。具有挑战性的大环化反应通过乌尔曼耦合成功完成。值得注意的是，二芳基醚型庚烷体系的固有环张力促进了大环框架内Z-烯烃的形成，该环张力优先稳定了这种特定构型。
