Revisiting Claims of the Iron-, Cobalt-, Nickel-, and Copper-Catalyzed Suzuki Biaryl Cross-Coupling of Aryl Halides with Aryl Boronic Acids

Revisiting Claims of the Iron-, Cobalt-, Nickel-, and Copper-Catalyzed Suzuki Biaryl Cross-Coupling of Aryl Halides with Aryl Boronic Acids
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重新审视铁、钴、镍和铜催化的芳基卤化物与芳基硼酸的铃木联芳基交叉偶联的主张

DOI:
10.1021/acs.organomet.9b00083
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发表时间:
2019
期刊:
影响因子:
2.8
通讯作者:
Tailor S
Tailor S
中科院分区:
化学2区
文献类型:
--
作者:
Tailor S

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感兴趣的是最近的报告令人惊讶的优异的活性的范围内的钴,铁,铜,镍基催化剂在铃木联芳基交叉偶联简单的芳基硼酸与芳基卤化物,我们进行了重新审查的合成的代表性的例子报告的预催化剂和它们的应用程序的催化反应。一种已报道的PNP−Fe钳形络合物被证明是起始材料的混合物;一种单席夫碱钴络合物实际上是双连接加合物,而一种单体铜(II)PNP钳形络合物是二聚或低聚铜(I)物质。在我们的手中,无论是这些复合物,也没有任何其他的选定的预催化剂的研究表明,在铃木交叉偶联反应的电子活化的芳基溴与苯基硼酸的任何活动。同时,将亲核试剂切换为BuLi活化的苯基硼酸频哪醇酯,用钴预催化剂得到了一些有希望的活性。
Intrigued by recent reports on the surprisingly excellent activity of a range of cobalt-, iron-, copper-, and nickel-based catalysts in the Suzuki biaryl cross-coupling of simple aryl boronic acids with aryl halides, we undertook a reexamination of the syntheses of representative examples of the reported precatalysts and their application to the catalytic reaction. A reported PNP−Fe pincer complex proved to be a mixture of starting materials; a mono-Schiff base cobalt complex in fact the bis-ligated adduct and a monomeric copper(II) PNP–pincer complex a di- or oligomeric copper(I) species. In our hands, neither these complexes nor any other of the selected precatalysts investigated showed any activity in a Suzuki cross-coupling reaction of an electronically activated aryl bromide with phenyl boronic acid. Meanwhile, switching the nucleophile to the BuLi-activated phenyl boronic pinacol ester gave some promising activity with cobalt precatalysts.
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