Acyl radical to rhodacycle addition and cyclization relay to access butterfly flavylium fluorophores.,Nature Communications

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Acyl radical to rhodacycle addition and cyclization relay to access butterfly flavylium fluorophores.
Nature Communications ( IF 14.7 ) Pub Date : 2019-12-11 , DOI: 10.1038/s41467-019-13611-6
Jiangliang Yin ₁ , Yuming Zhang ₁ , Jian Li ₁ , Lei Zhu ₂ , Yu Lan ₂ , Jingsong You ₁

Affiliation

Transition metal-catalyzed C-H activation and radical reactions are two versatile strategies to construct diverse organic skeletons. Here we show the construction of a class of flavylium fluorophores via the merge of radical chemistry and C-H activation starting from (hetero)aryl ketones and alkynes. This protocol is not only applicable to aryl ketones but also to heteroaryl ketones such as thiophene, benzothiophene and benzofuran, thus leading to structural diversity. Mechanism studies, including control experiments, intermediate separation, radical trapping, EPR and ESI-HRMS experiments, demonstrate that the key step lies in the addition of the acyl radical generated by the copper-catalyzed C-C bond cleavage of aryl ketone to the rhodacycle formed via the C-H activation of aryl ketone. The flavylium fluorophores feature butterfly symmetrical configuration, nearly planar skeleton and delocalized positive charge, and exhibit intriguing photophysical properties, such as tunable absorption and emission wavelengths and high quantum yields.

中文翻译：

酰基自由基可与Rhodacycle加成和环化中继，以获取蝶形黄酮荧光团。

过渡金属催化的CH活化和自由基反应是构建多种有机骨架的两种通用策略。在这里，我们通过自由基化学和CH活化（从（杂）芳基酮和炔烃开始）的合并显示了一类黄酮荧光团的构建。该方案不仅适用于芳基酮，而且适用于杂芳基酮，例如噻吩，苯并噻吩和苯并呋喃，因此导致结构多样性。包括对照实验，中间分离，自由基捕获，EPR和ESI-HRMS实验在内的机理研究表明，关键步骤在于将芳基酮的铜催化CC键裂解产生的酰基基团添加到通过芳基酮的CH活化。

更新日期：2019-12-11

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