Efficient access to materials-oriented aromatic alkynes via the mechanochemical Sonogashira coupling of solid aryl halides with large polycyclic conjugated systems.
Efficient access to materials-oriented aromatic alkynes via the mechanochemical Sonogashira coupling of solid aryl halides with large polycyclic conjugated systems.
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DOI：
10.1039/d1sc05257h
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发表时间：
2022-01-05
期刊：
影响因子：
8.4
通讯作者：
Ito H
中科院分区：
文献类型：
--
作者：
Gao Y;Feng C;Seo T;Kubota K;Ito H
Sonogashira偶联是制备含C(Sp)-C(Sp2)键的有机材料不可或缺的工具。提高这种方法的效率和通用性一直是材料科学中的一个重要研究课题。在这里，我们展示了高温球磨技术能够实现钯催化的固体芳基卤化物的高效Sonogashira偶联反应，这些固体芳基卤化物具有大的多芳香族结构，包括难溶的底物和未活化的芳基氯化物。事实上，这种新的方案提供了各种面向材料的多芳烃，在没有本体反应溶剂的情况下，在很短的反应时间内获得了优异的产率。值得注意的是，我们通过难溶的还原红1的机械力化学Sonogashira偶联合成了一种新的发光材料，与基于溶液的条件相比，产率要高得多。通过两个连续的机械力化学Sonogashira交叉偶联反应快速合成了荧光金属有机骨架(MOF)前驱体，进一步证明了该方法的实用性。本研究展示了球磨Sonogashira联轴器在制备材料导向的炔烃和发现新型功能材料方面的巨大潜力。利用高温球磨技术，实现了一种实用的芳香族卤化物Sonogashira交叉偶联的机械力化学方法，为合成面向材料的芳香烃提供了有效途径。
Sonogashira coupling represents an indispensable tool for the preparation of organic materials that contain C(sp)–C(sp2) bonds. Improving the efficiency and generality of this methodology has long been an important research subject in materials science. Here, we show that a high-temperature ball-milling technique enables the highly efficient palladium-catalyzed Sonogashira coupling of solid aryl halides that bear large polyaromatic structures including sparingly soluble substrates and unactivated aryl chlorides. In fact, this new protocol provides various materials-oriented polyaromatic alkynes in excellent yield within short reaction times in the absence of bulk reaction solvents. Notably, we synthesized a new luminescent material via the mechanochemical Sonogashira coupling of poorly soluble Vat Red 1 in a much higher yield compared to those obtained using solution-based conditions. The utility of this method was further demonstrated by the rapid synthesis of a fluorescent metal–organic framework (MOF) precursor via two sequential mechanochemical Sonogashira cross-coupling reactions. The present study illustrates the great potential of Sonogashira coupling using ball milling for the preparation of materials-oriented alkynes and for the discovery of novel functional materials. Using a high-temperature ball-milling technique, a practical mechanochemical protocol for the Sonogashira cross-coupling of polyaromatic halides was achieved, which provides efficient access to materials-oriented aromatic alkynes.
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影响因子：
2
作者：
Do, Jean-Louis;Friscic, Tomislav
通讯作者：
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影响因子：
9.8
作者：
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