利用二氧化碳自由基阴离子对 1,6-二烯进行反选择性羧基环化反应

IF 1.4 4区化学 Q3 CHEMISTRY, MULTIDISCIPLINARY

Chemistry Letters Pub Date : 2024-07-27 DOI:10.1093/chemle/upae149

Yan Song, Hiroki Hayashi, Saeesh R Mangaonkar, Tsuyoshi Mita

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引用次数: 0

摘要

由于二氧化碳自由基阴离子（CO2--）具有合成有价值有机化合物的潜力，因此它与烯烃的反应性备受关注。在此，我们报告了 CO2--与 1,6-二烯之间的反应，通过高度反式选择性的 5-外三环化反应生成 5 元内酰胺衍生物。羧基环化和加氢环化的综合产率高达 74%。计算研究表明，环化过程中的过渡态有利于反式构型而非顺式构型。这项工作为合成 N-杂环提供了新的见解。

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Trans-Selective Carboxylative Cyclization of 1,6-Dienes Using the CO2 Radical Anion

The reactivity of the carbon dioxide radical anion (CO2•−) toward alkenes has garnered remarkable attention owing to its potential to synthesize valuable organic compounds. Herein, we report the reactions between CO2•− and 1,6-dienes, yielding 5-membered lactam derivatives via highly trans-selective 5-exo-trig cyclization. Both carboxylative cyclization and hydrocyclization occur with up to 74% combined yield. Computational studies show that the transition state during cyclization favors the trans-configuration over cis. This work offers new insights into the synthesis of N-heterocycles.

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来源期刊

Chemistry Letters 化学-化学综合

CiteScore

3.00

自引率

6.20%

发文量

260

审稿时长

1.2 months

期刊介绍： Chemistry Letters covers the following topics: -Organic Chemistry- Physical Chemistry- Inorganic Chemistry- Analytical Chemistry- Materials Chemistry- Polymer Chemistry- Supramolecular Chemistry- Organometallic Chemistry- Coordination Chemistry- Biomolecular Chemistry- Natural Products and Medicinal Chemistry- Electrochemistry