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Theoretical Study of C-alpha-H Hydroxylation of 4-Chloro-N-cyclopropyl-N-isopropylaniline Catalyzed by Cytochrome P450
Li Dongmei; Liu Jianyong
KeywordDensity Functional Theory Transition State Hydrogen Atom Transfer Energy Barrier Reaction Rate Reaction Mechanism
Source PublicationCHINESE JOURNAL OF CATALYSIS
2011-07-01
DOI10.3724/SP.J.1088.2011.10303
Volume32Issue:7Pages:1208-1213
Indexed BySCI
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences ; Technology
WOS SubjectChemistry, Applied ; Chemistry, Physical ; Engineering, Chemical
WOS Research AreaChemistry ; Engineering
WOS KeywordISOTOPE-EFFECT PROFILES ; DENSITY-FUNCTIONAL THERMOCHEMISTRY ; OXIDATIVE N-DEMETHYLATION ; SUBSTITUTED N,N-DIMETHYLANILINES ; ELECTRON-TRANSFER ; ABSTRACTION MECHANISM ; HYDROGEN ABSTRACTION ; REACTIVITY PATTERNS ; CYCLOPROPYL GROUP ; DEALKYLATION
AbstractThe 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.
Language英语
WOS IDWOS:000293319300016
Citation statistics
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/142662
Collection中国科学院大连化学物理研究所
AffiliationChinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China
Recommended Citation
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.
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