解码愈创木酚内酯生物合成：假愈创木酚内酯和seco愈创木酚内酯的合成见解

IF 5 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Letters Pub Date : 2025-05-13 DOI:10.1021/acs.orglett.5c0048510.1021/acs.orglett.5c00485

Maria Kourgiantaki, and , Alexandros L. Zografos*,

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引用次数: 0

摘要

导致假愈创木酚内酯和仲愈创木酚内酯的生物合成途径尚不清楚。在这项工作中，我们证明了高度氧化的8,12-愈创木酚内酯可以作为前所未有的前体，实现化学选择性，一步获得假愈创木酚内酯，次愈创木酚内酯和黄烷醇型倍半萜。关键的机制见解揭示了过氧化氢取代基对愈木酚内酯核心和立体电子因素在控制反应结果中的关键作用。这些发现揭示了愈创木酚内酯的选择性，可能反映了实际的生物合成途径，为倍半萜类化合物合成中的氧化转化提供了转化潜力。

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Decoding Guaianolide Biosynthesis: Synthetic Insights into Pseudoguaianolides and Seco-Guaianolides

The biosynthetic pathways leading to pseudoguaianolides and seco-guaianolides remain unclear. In this work, we demonstrate that highly oxidized 8,12-guaianolides serve as unprecedented precursors, enabling chemoselective, one-step access to pseudoguaianolide, seco-guaianolide, and xanthanolide-type sesquiterpenoids. Key mechanistic insights reveal the pivotal role of peroxide substituents on the guaianolide core and stereoelectronic factors in controlling reaction outcomes. These findings shed light on guaianolide selectivity and may mirror actual biosynthetic pathways, offering transformative potential for oxidative transformations in sesquiterpenoid synthesis.

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来源期刊

Organic Letters 化学-有机化学

CiteScore

9.30

自引率

11.50%

发文量

1607

审稿时长

1.5 months

期刊介绍： Organic Letters invites original reports of fundamental research in all branches of the theory and practice of organic, physical organic, organometallic,medicinal, and bioorganic chemistry. Organic Letters provides rapid disclosure of the key elements of significant studies that are of interest to a large portion of the organic community. In selecting manuscripts for publication, the Editors place emphasis on the originality, quality and wide interest of the work. Authors should provide enough background information to place the new disclosure in context and to justify the rapid publication format. Back-to-back Letters will be considered. Full details should be reserved for an Article, which should appear in due course.