全氟烷基炔和苄胺的 [4+2] 去氟环化反应：元氟烷基吡啶-4-胺的合成

IF 4.9 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Letters Pub Date : 2025-03-28 DOI:10.1021/acs.orglett.5c01004

Xue-Ying Huang, Jia-Wei Chen, Ding-Peng Chen, Yi-Fan Ji, Zhi-Liang Shen, Mengtao Ma, Xue-Qiang Chu

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引用次数: 0

摘要

吡啶是一种特殊的杂环，通过选择性去氟官能化从多氟物质中产生氟化吡啶的能力是对它们的合成的新补充。本文描述了一种在无金属条件下对全氟烷基炔和苄胺进行的前所未有的[4+2]脱氟加成反应。利用全氟烷基烷相邻的两个位阻全氟烷基碳上的4个C(sp3) -F键的官能团功能化，合成了一系列具有良好官能团耐受性的间氟烷基化吡啶-4胺。机理研究揭示了一系列的氢胺化、连续去氟化、6π电环化、芳构化和胺化反应。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

[4+2] Defluorocycloaddition of Perfluoroalkyl Alkynes and Benzylamines: Synthesis of meta-Fluoroalkylated Pyridin-4-amines

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[4+2] Defluorocycloaddition of Perfluoroalkyl Alkynes and Benzylamines: Synthesis of meta-Fluoroalkylated Pyridin-4-amines

Pyridines represent privileged heterocycles, and the ability to produce fluorinated pyridines from polyfluorinated substances through selective defluorofunctionalization is a new addition to their synthesis. Herein, an unprecedented formal [4+2] defluorocycloaddition of perfluoroalkyl alkynes and benzylamines under metal-free conditions is described. By leveraging the functionalization of four C(sp³)–F bonds on two vicinal sterically hindered perfluoroalkyl carbons of perfluoroalkyl alkynes, a diverse array of meta-fluoroalkylated pyridin-4-amines were synthesized with good functional group tolerance. The mechanistic studies revealed a sequence of hydroamination, successive defluorination, 6π-electrocyclization, aromatization, and amination.

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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.