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题名: Theoretical Study of C-alpha-H Hydroxylation of 4-Chloro-N-cyclopropyl-N-isopropylaniline Catalyzed by Cytochrome P450
作者: Li Dongmei1;  Liu Jianyong1
关键词: density functional theory ;  transition state ;  hydrogen atom transfer ;  energy barrier ;  reaction rate ;  reaction mechanism
刊名: CHINESE JOURNAL OF CATALYSIS
发表日期: 2011-07-01
DOI: 10.3724/SP.J.1088.2011.10303
卷: 32, 期:7, 页:1208-1213
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences ;  Technology
类目[WOS]: Chemistry, Applied ;  Chemistry, Physical ;  Engineering, Chemical
研究领域[WOS]: Chemistry ;  Engineering
英文摘要: The reaction mechanism of C-alpha-H hydroxylation of 4-chloro-N-cyclopropyl-N-isopropylaniline catalyzed by cytochrome P450 was investigated using the density functional theory. The Becke's three-parameter hybrid exchange functional and the Lee-Yang-Parr correlation functional (B3LYP) were used in the structure optimization and single-point energy calculations. There are two C-alpha-H hydroxylation reaction pathways for 4-chloro-N-cyclopropyl-N-isopropylaniline catalyzed by P450. One is C-alpha-H hydroxylation at the cyclopropyl group, and the other is C-alpha-H hydroxylation at the isopropyl group. Our calculations demonstrate that the C-alpha-H activation at both the cyclopropyl group and the isopropyl group is a hydrogen atom transfer process, and the reaction is concerted. Since the C-alpha-H activation energy on the high-spin quartet state is much higher than that on the low-spin (LS) doublet state, the C-alpha-H hydroxylation proceeds in a spin-selective manner, mostly on the LS state. Comparison of the energy barriers for the two reaction pathways predicts a preponderance of C-alpha-H hydroxylation at the cyclopropyl group over that on the isopropyl group by roughly a ratio of 1.8:1, which means that the N-decyclopropylation branch is 64% and the N-deisopropylation branch is 36% during the dealkylation of 4-chloro-N-cyclopropyl-N-isopropylaniline. This is in agreement with former experimental results.
关键词[WOS]: ISOTOPE-EFFECT PROFILES ;  DENSITY-FUNCTIONAL THERMOCHEMISTRY ;  OXIDATIVE N-DEMETHYLATION ;  SUBSTITUTED N,N-DIMETHYLANILINES ;  ELECTRON-TRANSFER ;  ABSTRACTION MECHANISM ;  HYDROGEN ABSTRACTION ;  REACTIVITY PATTERNS ;  CYCLOPROPYL GROUP ;  DEALKYLATION
语种: 英语
WOS记录号: WOS:000293319300016
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/142662
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China

Recommended Citation:
Li Dongmei,Liu Jianyong. Theoretical Study of C-alpha-H Hydroxylation of 4-Chloro-N-cyclopropyl-N-isopropylaniline Catalyzed by Cytochrome P450[J]. CHINESE JOURNAL OF CATALYSIS,2011,32(7):1208-1213.
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