State Key Laboratory of Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, P. R. China.
State Key Laboratory of Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering, Wuhu Hospital Affiliated to East China Normal University, East China Normal University, Shanghai 200062, P. R. China.
J Am Chem Soc. 2023 Aug 9;145(31):16988-16994. doi: 10.1021/jacs.3c05455. Epub 2023 Jul 26.
The asymmetric total syntheses of C19 diterpenoids, bearing a unique cycloheptene A ring with a chiral methyl group at C-12, were disclosed based on a universal strategy. Six members, including cephinoid P, cephafortoid A, 14--cephafortoid A and fortalpinoids M-N, P, were accomplished for the first time. The concise approach relies on two crucial steps: (1) a Nicholas/Hosomi-Sakurai cascade reaction was developed to efficiently generate the cycloheptene ring bearing a chiral methyl group; (2) an intramolecular Pauson-Khand reaction was followed to facilitate the construction of the complete skeleton of target molecules. Our studies provide a new strategy for the synthetic analysis of diterpenoids and structurally related polycyclic natural products.
基于通用策略，揭示了具有独特的环己烯 A 环和手性甲基在 C-12 位的 C19 二萜的不对称全合成。首次完成了包括 cephinoid P、cephafortoid A、14--cephafortoid A 和 fortalpinoids M-N、P 在内的 6 个成员。简洁的方法依赖于两个关键步骤：（1）开发了 Nicholas/Hosomi-Sakurai 级联反应，有效地生成了具有手性甲基的环己烯环；（2）随后进行了分子内 Pauson-Khand 反应，有利于目标分子完整骨架的构建。我们的研究为二萜和结构相关的多环天然产物的合成分析提供了新策略。
