使用 RhCl3·3H2O 作为催化剂的二重 C−H/C−H 交叉偶联：N-（杂）芳基咪唑鎓盐和（杂）芳烃的直接融合,Journal of the American Chemical Society

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使用 RhCl3·3H2O 作为催化剂的二重 C−H/C−H 交叉偶联：N-（杂）芳基咪唑鎓盐和（杂）芳烃的直接融合
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2018-08-31 , DOI: 10.1021/jacs.8b07485
Zhijie She ₁ , Yi Wang ₂ , Deping Wang ₁ , Yinsong Zhao ₁ , Tianbao Wang ₁ , Xuesong Zheng ₁ , Zhi-Xiang Yu ₂ , Ge Gao ₁ , Jingsong You ₁

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由于 Cp* 的特殊配体效应，[Cp*RhCl2]2 是铑催化螯合辅助 CH/CH 交叉偶联反应中最常用的催化剂。在本文中，提出并评估了使用简单的无机铑盐 RhCl3·3H2O 作为催化剂的新概念，该概念利用 Rh 与（杂）芳族反应组分的原位 π 配位来稳定 Rh 中间体。我们的研究不仅证明了这一概念的可行性，而且还公开了 N-（杂）芳基咪唑鎓盐与各种（杂）芳烃的新型 2 倍 CH/CH 交叉偶联反应，以获得水溶性、荧光、阳离子和平面多环杂芳族分子，其中RhCl3·3H2O优于[Cp*RhCl2]2。机理实验和 DFT 计算表明，这种连续的四重 CH 活化反应由两种不同的 CH 活化模式组成，即协同金属化-去质子化 (CMD) 和氧化加成。值得注意的是，这是首次报道通过在双（杂）芳基形成中氧化加成到 RhI 并释放氢来激活 CH 键。最后，利用中性（杂）芳烃和阴离子Cp*的不同配体电化学参数来解释RhCl3·3H2O和[Cp*RhCl2]2的不同催化行为。

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Two-Fold C−H/C−H Cross-Coupling Using RhCl3·3H2O as the Catalyst: Direct Fusion of N-(Hetero)arylimidazolium Salts and (Hetero)arenes

[Cp*RhCl2]2 is the most prevailing catalyst employed for rhodium-catalyzed chelation-assisted C-H/C-H cross-coupling reactions due to the special ligand effect of Cp*. In this article, a novel concept of using a simple inorganic rhodium salt, RhCl3·3H2O, as the catalyst by taking advantage of in situ π-coordination to Rh with a (hetero)aromatic reaction component to stabilize Rh intermediates is proposed and evaluated. Our studies not only prove the feasibility of this concept but also disclose a novel 2-fold C-H/C-H cross-coupling reaction of N-(hetero)arylimidazolium salts with various (hetero)arenes to access water-soluble, fluorescent, cationic, and planar polycyclic heteroaromatic molecules, in which RhCl3·3H2O outperforms [Cp*RhCl2]2. Mechanistic experiments and DFT calculations reveal that this successive quadruple C-H activation reaction consists of two different C-H activation modes, i.e., concerted metalation-deprotonation (CMD) and oxidative addition. Notably, this is the first report of a C-H bond activation via oxidative addition to RhI in a bi(hetero)aryl formation with hydrogen evolution. Finally, the different ligand electrochemical parameters of neutral (hetero)arenes and anionic Cp* are used to explain the different catalytic behaviors of RhCl3·3H2O and [Cp*RhCl2]2.

更新日期：2018-08-31

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