Selective Pd-catalyzed oxidative coupling of anilides with olefins through C-H bond activation at room temperature
Selective Pd-catalyzed oxidative coupling of anilides with olefins through C-H bond activation at room temperature
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DOI：
10.1021/ja0176907
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发表时间：
2002-02-27
影响因子：
15
通讯作者：
van Leeuwen, PWNM
中科院分区：
文献类型：
--
作者：
Boele, MDK;van Strijdonck, GPF;van Leeuwen, PWNM
采用高通量实验方法，我们发现了苯胺衍生物与丙烯酸酯之间通过邻位C-−-H键活化发生的选择性温和的钯催化氧化偶联反应。该反应在酸性环境中进行，即使在室温下也可以进行，使用廉价的氧化剂(苯二酚)，产率可达91%。苯二酚还可能起到配位体的作用，稳定催化剂。根据反应的电子依赖性和观察到的动力学同位素效应(KH/Kd=3)，认为催化循环的关键步骤是[PdOAc]+络合物对芳烃π-体系的亲电攻击。
Using a high-throughput experimentation approach we found a selective and mild Pd-catalyzed oxidative coupling reaction between anilide derivatives and acrylates that occurs through ortho C−H bond activation. The reaction is carried out in an acidic environment and occurs even at room temperature with use of a cheap oxidant (benzoquinone) in yields up to 91%. The benzoquinone possibly also functions as a ligand, stabilizing the catalyst. From the electronic dependence of the reaction and the observed kinetic isotope effect (kH/kD= 3) the key step of the catalytic cycle is believed to be electrophilic attack by a [PdOAc]+complex on the π-system of the arene.