细胞苷元的简易合成方法以及曲霉香豆素 A 和 fusarimarin C 的首次全合成

IF 2.1 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron Pub Date : 2024-10-26 DOI:10.1016/j.tet.2024.134343

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引用次数: 0

摘要

本研究展示了首次全合成具有生物活性的异香豆素天仙子香豆素 A、扶桑香豆素 C 和细胞苷元的新颖、高效路线。这种方法的特点是，在 LiBr-LiTMP 复合物存在的情况下，利用二甲氧基丁二酸乙酯和乙醇酸乙酯的高难度交叉酯偶联，开创性地一步合成异香豆素。该工艺利用溴离子诱导的聚合作用来促进单锅串联反应序列：侧向石碳酸化、酰化、烯醇化和内酯化。这种创新方法能高效地直接生成异香豆素分子。随后的转化过程包括选择性 BBr3 介导的去甲基化、氧化和 Wittig 反应。所展示的简化合成路线包括：两步合成细胞苷元，四步合成曲霉香豆素 A 和扶桑香豆素 C，总产率分别为 37%、27% 和 27%。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

A short approach to cytogenin and first total synthesis of aspergisocoumarin A and fusarimarin C

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A short approach to cytogenin and first total synthesis of aspergisocoumarin A and fusarimarin C

A novel, efficient route to the first total synthesis of the bioactive isocoumarins aspergisocoumarin A, fusarimarin C and cytogenin is demonstrated. This approach features a groundbreaking single-step synthesis of isocoumarins utilizing a challenging cross-ester coupling of ethyl dimethoxy orsellinate and ethyl glycolate in the presence of a LiBr-LiTMP complex. The process leverages bromide ion-induced aggregation to facilitate a one-pot tandem reaction sequence: lateral lithiation, acylation, enolization, and lactonization. This innovative method directly produces the isocoumarin moiety with high efficiency. Subsequent transformations include selective BBr₃-mediated demethylation, oxidation, and Wittig reactions. The streamlined synthetic routes demonstrated: a two-step pathway to cytogenin and a four-step sequence to aspergisocoumarin A and fusarimarin C, achieving overall yields of 37 %, 27 %, and 27 % respectively.

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来源期刊

Tetrahedron 化学-有机化学

CiteScore

3.90

自引率

4.80%

发文量

439

审稿时长

34 days

期刊介绍： Tetrahedron publishes full accounts of research having outstanding significance in the broad field of organic chemistry and its related disciplines, such as organic materials and bio-organic chemistry. Regular papers in Tetrahedron are expected to represent detailed accounts of an original study having substantially greater scope and details than that found in a communication, as published in Tetrahedron Letters. Tetrahedron also publishes thematic collections of papers as special issues and ''Reports'', commissioned in-depth reviews providing a comprehensive overview of a research area.