Cu(II)-nitroxyl radicals as catalytic galactose oxidase mimics
Cu(II)-nitroxyl radicals as catalytic galactose oxidase mimics
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DOI：
10.1039/b305941c
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发表时间：
2003-01-01
影响因子：
3.2
通讯作者：
Sheldon, RA
中科院分区：
文献类型：
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作者：
Dijksman, A;Arends, IWCE;Sheldon, RA
CuCL-TEMPO催化的苯甲醇好氧氧化反应的Hammett相关性研究和初级动力学同位素效应的结果与氧铵反应的机理不一致。我们假设了一种铜介导的脱氢机制，在该机制中，TEMPO再生了活性的铜(II)物种。这种机制类似于观察到的半乳糖氧化酶及其模拟物。
Results from Hammett correlation studies and primary kinetic isotope effects for the CuCl - TEMPO catalysed aerobic benzyl alcohol oxidations are inconsistent with an oxoammonium based mechanism. We postulate a copper-mediated dehydrogenation mechanism, in which TEMPO regenerates the active Cu(II)-species. This mechanism is analogous to that observed for Galactose Oxidase and mimics thereof.