亲核苯基攻击3,6-二(2-吡啶基)-1,2-嘧啶引发的重排级联。

IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY
ACS Organic & Inorganic Au Pub Date : 2025-01-28 eCollection Date: 2025-04-02 DOI:10.1021/acsorginorgau.4c00070
Johannes Schöntag, Theresa Hettiger, William Roberts, Marcus Scheele, Markus Ströbele, Holger F Bettinger
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引用次数: 0

摘要

合成有机化学中的芳烃中间体为合成复杂的杂环结构提供了多种途径,在药物和材料科学中具有重要价值。通过单晶x射线晶体学和核磁共振波谱证实,我们提出了一个一步炔介导的反应,合成吡啶[1,2-a]吲哚,通过乙烯烯或1,2-苯基连接物与吡啶三唑连接。这种意想不到的重排在温和的条件下进行。考虑到在3,6-二-2-吡啶-1,2,4,5-四嗪与苯的反应中有5个键断裂,3个新键形成,收率为16%是合理的。芳烃前驱体上的富电子取代基破坏了产物的稳定性,而缺电子取代基则提高了产物的稳定性。DFT研究可以揭示这种重排的机制。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Rearrangement Cascade Initiated by Nucleophilic Benzyne Attack on 3,6-Di(2-pyridyl)-1,2-diazines.

Aryne intermediates in synthetic organic chemistry offer versatile routes to complex heterocyclic structures that are valuable in pharmaceuticals and materials science. We present a one-step aryne-mediated reaction to synthesize pyrido[1,2-a]indoles interconnected through vinylene or 1,2-phenylene linkers to pyridotriazoles using 2-pyridyl-substituted pyridazines and phthalazines as confirmed via single-crystal X-ray crystallography and NMR spectroscopy. This unexpected rearrangement proceeds under mild conditions. Considering that five bonds are broken and three new bonds are formed in the reaction between 3,6-di-2-pyridyl-1,2,4,5-tetrazine and benzyne, the yield of 16% is fair. Electron-rich substituents on aryne precursors destabilized the products, while electron-deficient substituents offered some stability improvements. DFT studies could reveal the mechanism of this rearrangement.

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来源期刊
ACS Organic & Inorganic Au
ACS Organic & Inorganic Au 有机化学、无机化学-
CiteScore
4.10
自引率
0.00%
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0
期刊介绍: ACS Organic & Inorganic Au is an open access journal that publishes original experimental and theoretical/computational studies on organic organometallic inorganic crystal growth and engineering and organic process chemistry. Short letters comprehensive articles reviews and perspectives are welcome on topics that include:Organic chemistry Organometallic chemistry Inorganic Chemistry and Organic Process Chemistry.
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