| Theoretic study of the reaction mechanism between （Me）3CO· radical and trans-3-hexene |
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| 作者姓名： | SHI GuoSheng DING YiHong |
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| 作者单位： | State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China |
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| 基金项目： | Supported by the National Natural Science Foundation of China (Grant Nos. 20103003 and 20573046), Excellent Young People Foundation of Jilin Province, China (Grant No. 20050103) and Program for New Century Excellent Talents in University (NCET) of China |
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| 摘 要： | The reaction mechanism between （Me）3CO· radical and trans-3-hexene in benzene was studied for the first time at the B3LYP/6-311＋＋G（d,p）//B3LYP/6-31G（d）＋ZPVE level. Two distinct elementary channels were identified as： （1） abstraction-addition; （2） addition-addition-elimination. Analysis of the potential energy surface demonstrates that for the title reaction, channels （1） and （2） have the major and minor contribution, respectively. Our calculated results can well explain the recently observed product distribution by Coseri et al. （J. Org. Chem. 2005, 70, 4629）. However, we found that the addition-abstraction channel proposed by Coseri et al. is kinetically infeasible.
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| 关 键 词： | 反转-3-己烯 电位 反应机理 理论学习 自由基 |
| 收稿时间： | 2008-01-02 |
| 修稿时间： | 2008-04-06 |
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