Substituent effects upon the catalytic activity of aromatic cyclic seleninate esters and spirodioxyselenuranes that act as glutathione peroxidase mimetics
Substituent effects upon the catalytic activity of aromatic cyclic seleninate esters and spirodioxyselenuranes that act as glutathione peroxidase mimetics
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DOI：
10.1021/jo800381s
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发表时间：
2008-06-06
影响因子：
3.6
通讯作者：
Back, Thomas G.
中科院分区：
文献类型：
--
作者：
Press, David J.;Mercier, Eric A.;Back, Thomas G.
取代基的影响进行了研究，在一系列的芳香族环硒酸酯和spirodioxyselenuranes作为模拟物的抗氧化剂硒酶谷胱甘肽过氧化物酶的功能。甲氧基取代的硒铀烷被证明是最有效的催化剂，用于还原过氧化氢与苄硫醇，和反应速率提高两个类的供电子取代基。Hammett图表明，ρ = -0.45和-3.1的硒酸盐和硒铀烷，分别，这表明在硒的氧化是其催化循环中的速率决定步骤。
Substituent effects were studied in a series of aromatic cyclic seleninate esters and spirodioxyselenuranes that function as mimetics of the antioxidant selenoenzyme glutathione peroxidase. The methoxy-substituted selenurane proved the most efficacious catalyst for the reduction of hydrogen peroxide with benzyl thiol, and the reaction rates were enhanced for both classes by electron-donating substituents. Hammett plots indicated rho = -0.45 and -3.1 for the seleninates and selenuranes, respectively, suggesting that oxidation at Se is the rate-determining step in their catalytic cycles.