Visible-Light-Mediated Cyclization of Intramolecular Electron Donor–Acceptor (EDA) Complexes and Its Application in the Total Synthesis of Corynanthe-Type Alkaloids

IF 4.7 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Letters Pub Date : 2026-10-16 Epub Date: 2026-10-02 DOI:10.1021/acs.orglett.6c03905

Xian Lu, Yuecai Chang, Guangsong Ge, Lihua Huang, Beiling Gao

引用次数: 0

Abstract

A visible-light-driven one-pot decarboxylative cyclization cascade via an intramolecular electron donor–acceptor (EDA) complex is reported. By covalently tethering an indole donor and an NHPI ester acceptor with an alkyl linker, this strategy enables efficient assembly of the signature 6/5/6/6 tetracyclic skeleton of corynanthe-type monoterpene indole alkaloids under mild, metal- and photocatalyst-free neutral conditions. The transformation features a broad substrate scope (22 examples), excellent yields (68–98%), and facile gram-scale scalability. Using this reaction as the key step, we achieved the enantioselective total synthesis of (+)-hirsutinol and (−)-dihydrocorynantheol in 8 linear steps, which represents, to the best of our knowledge, the first application of an intramolecular EDA strategy in the total synthesis of indole alkaloids.

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可见光介导的分子内电子给受体（EDA）配合物环化及其在芫荽型生物碱全合成中的应用

摘要报道了一种通过分子内电子供体-受体（EDA）复合物的可见光驱动的一锅脱羧环化级联反应。通过将吲哚给体和NHPI酯受体与烷基连接共价连接，该策略能够在温和、无金属和光催化剂的中性条件下，高效地组装出香雀型单萜吲哚生物碱的6/5/6/6四环骨架。该转换具有广泛的衬底范围（22个示例），出色的收率（68-98%）和易于克级可扩展性。以该反应为关键步骤，我们通过8个线性步骤实现了(+)-hirsutinol和(−)-dihydrocorynantheol的对映选择性全合成，据我们所知，这是分子内EDA策略在吲哚类生物碱全合成中的首次应用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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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.