A novel approach to the tetracyclic frameworks of anislactone-type sesquiterpenoids†

Long He , Xiaocheng Zhang , Sen Li , Xuexue Tian , Yimeng Han , Haitao Xie , Weiqing Xie
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Abstract

Herein, we present a novel approach to construct the A-B-C-D ring system of anislactone-type sesquiterpenoids. This innovative strategy involves a H2O2-mediated oxidative ring contraction reaction to form a 5/5 fused skeleton, while simultaneously generating contiguous quaternary carbon centers (CQCCs). Additionally, γ-lactones (A- and D-rings) are assembled through Pummerer reaction initiated cyclization and sequential Mukaiyama hydration/translactonization, respectively. Despite our efforts to introduce a hydroxyl group at C7 via C–H oxidation, these endeavors ultimately proved unsuccessful.

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研究茴香内酯类四环框架的新方法
在此,我们提出了一种构建苯甲内酯类倍半萜 A-B-C-D 环系统的新方法。这种创新策略涉及 H2O2- 介导的氧化缩环反应,以形成 5/5 融合骨架,同时生成连续的季碳中心 (CQCC)。此外,γ-内酯(A 环和 D 环)分别通过普默尔反应引发的环化和顺序的向山水合/反式内酯化组装而成。尽管我们努力通过 C-H 氧化在 C7 处引入羟基,但这些努力最终都没有成功。
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