Metal-Free Transfer C-H Borylation of Substituted Thiophenes
Metal-Free Transfer C-H Borylation of Substituted Thiophenes
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DOI：
10.1002/zaac.202300006
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发表时间：
2023-03-24
影响因子：
1.4
通讯作者：
Fontaine, Frederic-Georges
中科院分区：
文献类型：
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作者：
Desrosiers, Vincent;Gaudy, Audrey;Fontaine, Frederic-Georges
噻吩类化合物是医药化学和材料化学领域的重要化学结构单元。因此，这些单元的C-H官能化对于开发新的应用至关重要。本文报道了噻吩类化合物的C-H硼基化反应。当在C2-取代的噻吩上进行时，该反应对于C5上的硼基化是选择性的，而C3-取代的噻吩在C2上硼基化，这是来自报道的通常优选在C5位置硼基化的C-H硼基化方法的互补选择性。对催化体系进行了优化。该反应被证明可以与电子多样的噻吩一起工作，并且也与敏感的官能团相容。计算研究的反应机制表明，刘易斯对C-H活化机制与动力学驱动的选择性。本文开发的方法是一种经济的途径，用于制备C2-硼基化C3-取代噻吩。
Thiophenes are crucial chemical building blocks in the fields of medicinal and material chemistry. As such, the C-H functionalization of these units is of key importance for developing novel applications. Herein, we report the C-H borylation of thiophenes using metal-free transfer C-H borylation. When performed on C2-substituted thiophenes, the reaction is selective for the borylation on C5, while C3-substituted thiophenes are borylated on C2, a complementary selectivity from reported C-H borylation approaches that typically prefer to borylate at the C5 position. An optimization of the catalytic system was performed. The reaction was shown to work with electronically diverse thiophenes and was also compatible with sensitive functional groups. Computational investigation of the reaction mechanism suggests a Lewis pair C-H activation mechanism with a selectivity that is kinetically driven. The methodology developed herein is an economical pathway for the preparation of C2-borylated C3-substituted thiophenes.