Selective Mechanochemical Monoarylation of Unbiased Dibromoarenes by in Situ Crystallization
Selective Mechanochemical Monoarylation of Unbiased Dibromoarenes by in Situ Crystallization
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DOI：
10.1021/jacs.0c01739
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发表时间：
2020-06-03
影响因子：
15
通讯作者：
Ito, Hajime
中科院分区：
文献类型：
--
作者：
Seo, Tamae;Kubota, Koji;Ito, Hajime
在机械化学条件下，钯催化液体、无偏置二溴芳烃的Suzuki-Miyaura交叉偶联反应选择性地产生单芳化产物。晶体单芳基化产物相对于液体起始材料的反应活性较低，主要归因于前者在反应混合物中的低扩散效率，从而导致选择性单芳基化。目前的研究揭示了一种新的方法，利用固体中的原位相变来设计通过传统的基于溶液的合成难以实现的选择性有机转化。
Palladium-catalyzed Suzuki-Miyaura cross-coupling reactions of liquid, unbiased dibromoarenes under mechanochemical conditions selectively afford the monoarylated products. The lower reactivity of the crystalline monoarylated products relative to the liquid starting materials should be attributed predominantly to the low diffusion efficiency of the former in the reaction mixture, which results in a selective monoarylation. The present study sheds light on a novel approach using in situ phase transitions in solids to design selective organic transformations that are difficult to achieve via conventional solution-based synthesis.