Theoretical Study of C-alpha-H Hydroxylation of 4-Chloro-N-cyclopropyl-N-isopropylaniline Catalyzed by Cytochrome P450
文献类型：期刊论文
| 作者 | Li Dongmei; Liu Jianyong |
| 刊名 | chinese journal of catalysis
 |
| 出版日期 | 2011-07-01 |
| 卷号 | 32期号:7页码:1208-1213 |
| 关键词 | density functional theory transition state hydrogen atom transfer energy barrier reaction rate reaction mechanism |
| 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. |
| 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 |
| 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 |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS记录号 | WOS:000293319300016 |
| 公开日期 | 2015-11-17 |
| 源URL | [http://159.226.238.44/handle/321008/142662]  |
| 专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
| 作者单位 | Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China |
| 推荐引用方式 GB/T 7714 | 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. |
| APA | Li Dongmei,&Liu Jianyong.(2011).Theoretical Study of C-alpha-H Hydroxylation of 4-Chloro-N-cyclopropyl-N-isopropylaniline Catalyzed by Cytochrome P450.chinese journal of catalysis,32(7),1208-1213. |
| MLA | Li Dongmei,et al."Theoretical Study of C-alpha-H Hydroxylation of 4-Chloro-N-cyclopropyl-N-isopropylaniline Catalyzed by Cytochrome P450".chinese journal of catalysis 32.7(2011):1208-1213. |
入库方式： OAI收割
来源：大连化学物理研究所
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