Division of Applied Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo, Hokkaido 060-8628, Japan.
Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo, Hokkaido 060-8628, Japan.
J Am Chem Soc. 2020 Jun 3;142(22):9884-9889. doi: 10.1021/jacs.0c01739. Epub 2020 May 4.
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 phase transitions in solids to design selective organic transformations that are difficult to achieve via conventional solution-based synthesis.
钯催化的无偏见液体二溴代芳烃的 Suzuki-Miyaura 交叉偶联反应在机械化学条件下选择性地得到单芳基产物。相对于液态的起始原料，结晶单芳基产物的反应性较低，这主要归因于前者在反应混合物中的扩散效率较低，从而导致选择性单芳基化。本研究揭示了一种利用固体相转变设计选择性有机转化的新方法，这些转化通过传统的基于溶液的合成方法难以实现。
