An Electron‐Deficient CpE Iridium(III) Catalyst: Synthesis, Characterization, and Application to Ether‐Directed C-H Amidation
An Electron‐Deficient CpE Iridium(III) Catalyst: Synthesis, Characterization, and Application to Ether‐Directed C-H Amidation
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缺电子 CpE 铱 (III) 催化剂：合成、表征及其在醚定向 C-H 酰胺化中的应用
DOI：
10.1002/anie.202301259
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Matsunaga Shigeki
中科院分区：
文献类型：
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作者：
Tomita Eiki;Kojima Masahiro;Nagashima Yuki;Tanaka Ken;Sugiyama Haruki;Segawa Yasutomo;Furukawa Atsushi;Maenaka Katsumi;Maeda Satoshi;Yoshino Tatsuhiko;Matsunaga Shigeki
报道了具有缺电子环戊二烯基配体 ([CpEIrI2]2) 的铱 (III) 催化剂的合成、表征和催化性能。 [CpEIrI2]2 催化剂是通过 CpEligand 的前体与 [Ir(cod)OAc]2 络合，然后氧化、脱甲硅烷基化和去除 COD 配体来合成的。缺电子的[CpEIrI2]2催化剂在弱配位醚导向基团的协助下实现了CH酰胺化反应。实验机理研究和DFT计算表明，[CpEIrI2]2的高催化性能归因于其缺电子性质，它加速了CH活化和IrV-氮烯化合物的形成。
The synthesis, characterization, and catalytic performance of an iridium(III) catalyst with an electron‐deficient cyclopentadienyl ligand ([CpEIrI2]2) are reported. The [CpEIrI2]2catalyst was synthesized by complexation of a precursor of the CpEligand with [Ir(cod)OAc]2, followed by oxidation, desilylation, and removal of the COD ligand. The electron‐deficient [CpEIrI2]2catalyst enabled C−H amidation reactions assisted by a weakly coordinating ether directing group. Experimental mechanistic studies and DFT calculations suggested that the high catalytic performance of [CpEIrI2]2is due to its electron‐deficient nature, which accelerates both C−H activation and IrV‐nitrenoid formation.