百利草素A的克级全合成。

IF 14.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of the American Chemical Society Pub Date : 2025-06-25 DOI:10.1021/jacs.5c07921

Liangchao Zhu, Jinrui Li, Zhaohong Lu

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引用次数: 0

摘要

Illisimonin A是一种结构复杂的倍半萜类化合物，从illium属植物中分离出来，具有一个由7个连续的完全取代的手性季碳中心组成的5/5/5/5五环支架。在此，我们报道了在14个步骤中实现（±）-Illisimonin a的克级全合成。该策略方法具有几个关键转化：(1)涉及五氟烯的分子内[6 + 2]环加成，可快速组装线性5/5/5三环核心；(2)涉及五氟烯的分子内烷基化，可构建多环框架；(3)用于精确氧化态安装的亚硝基- diols - alder反应，以及(4)后期ru催化的氧化内酯化。

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Gram-Scale Total Synthesis of Illisimonin A.

Illisimonin A, a structurally complex sesquiterpenoid isolated from the Illicium genus, possesses a 5/5/5/5/5 pentacyclic scaffold featuring seven contiguous, fully substituted chiral quaternary carbon centers. Herein, we report a gram-scale total synthesis of (±)-Illisimonin A achieved in 14 steps. The strategic approach features several key transformations: (1) a pentafulvene-involved intramolecular [6 + 2] cycloaddition that rapidly assembles the linear 5/5/5 tricyclic core, (2) a pentafulvene-involved intramolecular alkylation enabling polycyclic framework construction, (3) a nitroso-Diels-Alder reaction for precise oxidation state installation, and (4) a late-stage Ru-catalyzed oxidative lactonization.

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来源期刊

Journal of the American Chemical Society 化学-化学综合

CiteScore

24.40

自引率

6.00%

发文量

2398

审稿时长

1.6 months

期刊介绍： The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.