Yi Jiuzhou, He Min, Zhang Yan, Yu Pengfei, Xie Xingang, Li Huilin, She Xuegong
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 Gansu, P. R. China.
Org Lett. 2024 Jun 21;26(24):5146-5150. doi: 10.1021/acs.orglett.4c01572. Epub 2024 Jun 10.
We report herein the total syntheses of three marsupellin-family sesquiterpenoids, (±)-acetoxymarsupellone and (±)-marsupellins B and D, in 14-19 steps from our known precursor, making marsupellin A also accessible from marsupellin B through a known procedure. The critical tricyclic framework bearing the challenging C7 bridgehead all-carbon quaternary center is strategically constructed through a Ti-mediated reductive cyclization and semipinacol rearrangement sequence. This study provides a general approach to the syntheses of (-)longipinane-type molecules.
我们在此报告了三种袋地钱素家族倍半萜类化合物，即（±）-乙酰氧基袋地钱酮以及（±）-袋地钱素B和D的全合成，它们由我们已知的前体经14至19步反应合成，这也使得通过已知方法从袋地钱素B获得袋地钱素A成为可能。带有具有挑战性的C7桥头全碳季碳中心的关键三环骨架是通过钛介导的还原环化和半频哪醇重排序列策略性构建的。本研究为（-）长叶蒎烷型分子的合成提供了一种通用方法。
