Insight into the Reactivity Profile of Solid-State Aryl Bromides in Suzuki-Miyaura Cross-Coupling Reactions Using Ball Milling
Insight into the Reactivity Profile of Solid-State Aryl Bromides in Suzuki-Miyaura Cross-Coupling Reactions Using Ball Milling
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DOI：
10.1055/a-1748-3797
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发表时间：
2022-06-01
期刊：
影响因子：
2
通讯作者：
Ito, Hajime
中科院分区：
文献类型：
--
作者：
Kubota, Koji;Kondo, Keisuke;Ito, Hajime
尽管最近在使用球磨的固态有机合成方面取得了进展，但对固态基质的独特反应性的洞察力（通常与溶液中的反应性不同）却很少被探索。在这项研究中，我们研究了固态Suzuki-Miyaura交叉偶联反应中芳基卤的反应性和熔点之间的关系以及反应温度对这些过程的影响。我们发现，具有高熔点的芳基卤化物在室温附近的固态交叉偶联反应中表现出显着低的反应活性，但反应温度的升高显着加快了反应。考虑到反应温度远低于这些底物的熔点，加速效应最有可能归因于固态底物分子之间的分子间相互作用的减弱。本研究提供了重要的观点，合理设计高效的固态有机转化球磨。
Despite recent advances in solid-state organic synthesis using ball milling, insight into the unique reactivity of solid-state substrates, which is often different from that in solution, has been poorly explored. In this study, we investigated the relationship between the reactivity and melting points of aryl halides in solid-state Suzuki-Miyaura cross-coupling reactions and the effect of reaction temperature on these processes. We found that aryl halides with high melting points showed significantly low reactivity in the solid-state cross-coupling near room temperature, but the reactions were notably accelerated by increasing the reaction temperature. Given that the reaction temperature is much lower than the melting points of these substrates, the acceleration effect is most likely ascribed to the weakening of the intermolecular interactions between the substrate molecules in the solid state. The present study provides important perspectives for the rational design of efficient solid-state organic transformations using ball milling.