Kinetic isotope effect is a sensitive probe of spin state reactivity in C-H hydroxylation of N,N-dimethylaniline by cytochrome P450

被引：72

作者：

Li, CS

Wu, W ^{[1
]}

Kumar, D

Shaik, S

机构：

[1] Xiamen Univ, State Key Lab Phys Chem & Solid Surf, Ctr Theoret Chem, Xiamen 361005, Peoples R China

[2] Xiamen Univ, Dept Chem, Xiamen 361005, Peoples R China

[3] Hebrew Univ Jerusalem, Dept Chem, IL-91904 Jerusalem, Israel

[4] Hebrew Univ Jerusalem, Lise Meitner Minerva Ctr Computat Quantum Chem, IL-91904 Jerusalem, Israel

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2006年 / 128卷 / 02期

关键词：

D O I：

10.1021/ja055987p

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

This paper presents DFT calculations of C-H hydroxylation of N,N-dimethylaniline by Compound I (Cpd I) of cytochrome P450. The reaction involves two processes nascent from the two spin states of Cpd I, the low-spin (LS) and high-spin (HS) states. The calculations demonstrate that the kinetic isotope effects (KIEs) of the two processes are very different, and only KIELS fits the experimental datum. As such, KIE can be a sensitive probe of spin state reactivity. Copyright © 2006 American Chemical Society.

引用

页码：394 / 395

页数：2

共 26 条

[1] Revisiting the mechanism of P450 enzymes with the radical clocks norcarane and spiro[2,5]octane [J].