Investigations into the mechanism of copper-mediated Glaser-Hay couplings using electrochemical techniques.
Investigations into the mechanism of copper-mediated Glaser-Hay couplings using electrochemical techniques.
复制标题
使用电化学技术研究铜介导的 Glaser-Hay 偶联的机制。
DOI：
10.1039/c9fd00031c
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发表时间：
2019
影响因子：
3.4
通讯作者：
Seavill PW
中科院分区：
文献类型：
--
作者：
Seavill PW
铜介导的C-C键形成反应的机制被称为C-H偶联（炔二聚）已使用电化学技术进行了研究。在有机碱DABCO存在下，对铜或镀铜石墨电极施加氧化电位，导致苯乙炔以良好的产率二聚。进一步的机理研究表明，该反应介质导致双核Cu（I）络合物的组装，尽管先前报道过，但从未显示出对C-C键形成具有催化性能。该复合物让人想起在Bohlmann模型中提出的Bohlmann-Hay反应，并因此赋予该提出的机制高于替代提出的单核催化循环的权重。
The mechanism of the copper mediated C–C bond forming reaction known as Glaser–Hay coupling (alkyne dimerization) has been investigated using electrochemical techniques. Applying an oxidative potential to a copper or copper-coated graphite electrode in the presence of the organic base DABCO results in the dimerization of phenylacetylene in good yield. Further mechanistic investigation has shown that this reaction medium results in the assembly of a dinuclear Cu(I) complex which, although previously reported, has never been shown to have catalytic properties for C–C bond formation. The complex is reminiscent of that proposed in the Bohlmann model for the Glaser–Hay reaction and as such lends weight to this proposed mechanism above the alternative proposed mononuclear catalytic cycle.