Tunneling Effect That Changes the Reaction Pathway from Epoxidation to Hydroxylation in the Oxidation of Cyclohexene by a Compound I Model of Cytochrome P450 | |
Department | 苏州研究院 |
Ranjana Gupta1; Li, Xiao-Xi1,2; Kyung-Bin Cho1; Guo, Mian1; Lee, Yong-Min1; Wang Y(王永)2; Shunichi Fukuzumi1,3; Wonwoo Nam1,2; Wang Y(王永) | |
The second department | osso国家重点实验室 |
2017 | |
Source Publication | Journal of Physical Chemistry Letters |
ISSN | 1948-7185 |
Volume | 8Issue:7Pages:1557-1561 |
Abstract | The rate constants of the C═C epoxidation and the C–H hydroxylation (i.e., allylic C–H bond activation) in the oxidation of cyclohexene by a high-valent iron(IV)–oxo porphyrin π-cation radical complex, [(TMP•+)FeIV(O)(Cl)] (1, TMP = meso-tetramesitylporphyrin dianion), were determined at various temperatures by analyzing the overall rate constants and the products obtained in the cyclohexene oxidation by 1, leading us to conclude that reaction pathway changes from the C═C epoxidation to C–H hydroxylation by decreasing reaction temperature. When cyclohexene was replaced by deuterated cyclohexene (cyclohexene-d10), the epoxidation pathway dominated irrespective of the reaction temperature. The temperature dependence of the rate constant of the C–H hydroxylation pathway in the reactions of cyclohexene and cyclohexene-d10 by 1 suggests that there is a significant tunneling effect on the hydrogen atom abstraction of allylic C–H bonds of cyclohexene by 1, leading us to propose that the tunneling effect is a determining factor for the switchover of the reaction pathway from the C═C epoxidation pathway to the C–H hydroxylation pathway by decreasing reaction temperature. By performing density functional theory (DFT) calculations, the reaction energy barriers of the C═C epoxidation and C–H bond activation reactions by 1 were found to be similar, supporting the notion that small environmental changes, such as the reaction temperature, can flip the preference for one reaction to another. |
Subject Area | 物理化学与绿色催化 |
DOI | 10.1021/acs.jpclett.7b00461 |
Funding Organization | the NRF of Korea through the CRI (NRF-2012R1A3A2048842 to W.N.);GRL (NRF-2010-00353 to W.N.);MSIP (NRF-2013R1A1A2062737 to K-B.C.);JSPS KAKENHI (No. 16H02268 to S.F.) |
Indexed By | SCI |
If | 9.353 |
Language | 英语 |
compositor | 第二作者单位 |
Citation statistics | |
Document Type | 期刊论文 |
Identifier | http://ir.licp.cn/handle/362003/21777 |
Collection | 苏州研究院 羰基合成与选择氧化国家重点实验室(OSSO) |
Corresponding Author | Shunichi Fukuzumi; Wonwoo Nam; Wang Y(王永) |
Affiliation | 1.Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea 2.Chinese Acad Sci, LICP, Suzhou Res Inst LICP, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China 3.Meijo Univ, Japan Sci & Technol Agcy JST, SENTAN, Fac Sci & Engn, Nagoya, Aichi 4688502, Japan |
Recommended Citation GB/T 7714 | Ranjana Gupta,Li, Xiao-Xi,Kyung-Bin Cho,et al. Tunneling Effect That Changes the Reaction Pathway from Epoxidation to Hydroxylation in the Oxidation of Cyclohexene by a Compound I Model of Cytochrome P450[J]. Journal of Physical Chemistry Letters,2017,8(7):1557-1561. |
APA | Ranjana Gupta.,Li, Xiao-Xi.,Kyung-Bin Cho.,Guo, Mian.,Lee, Yong-Min.,...&王永.(2017).Tunneling Effect That Changes the Reaction Pathway from Epoxidation to Hydroxylation in the Oxidation of Cyclohexene by a Compound I Model of Cytochrome P450.Journal of Physical Chemistry Letters,8(7),1557-1561. |
MLA | Ranjana Gupta,et al."Tunneling Effect That Changes the Reaction Pathway from Epoxidation to Hydroxylation in the Oxidation of Cyclohexene by a Compound I Model of Cytochrome P450".Journal of Physical Chemistry Letters 8.7(2017):1557-1561. |
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