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个人信息Personal Information
教授
博士生导师
硕士生导师
主要任职：Director, State Key laboratory of Fine Chemicals
其他任职：精细化工国家重点实验室主任、国务院学科评议组成员
性别：男
毕业院校：大连理工大学
学位：博士
所在单位：化工学院
学科：应用化学. 精细化工. 化学生物学
办公地点：大连理工大学精细化工国家重点实验室
西部校区化工实验楼F-202#
http://peng-group.dlut.edu.cn/
联系方式：大连理工大学精细化工国家重点实验室 西部校区化工实验楼F-202 辽宁省大连市高新区凌工路2号，大连116024 Tel: 0411-84986306; Fax: 0411-84986292；课题组网址：http://peng-group.dlut.edu.cn/
电子邮箱：pengxj@dlut.edu.cn
A DFT study of Diels-Alder reactions of o-quinone methides and various substituted ethenes: Selectivity and reaction mechanism
点击次数：
论文类型：期刊论文
发表时间：2005-06-24
发表刊物：JOURNAL OF ORGANIC CHEMISTRY
收录刊物：SCIE、EI、Scopus
卷号：70
期号：13
页面范围：4910-4917
ISSN号：0022-3263
摘要：The Diels-Alder (DA) reactions of various substituted ethenes (methyl vinyl ether (MVE), styrene, and methyl vinyl ketone (MVK)) with o-quinone methides (o-QM) are studied by means of density functional theory (DFT) at the B3LYP/6-31G(d,p) level. On the basis of analysis for frontier molecular orbital and comparison of the activation energies for different reaction pathways, the ortho attack modes present transition structures more stable than the meta ones. The reactivity, ortho selectivity, and asynchronicity are enhanced with the increase of the electron-releasing character of the substitute on ethene fragment. The discussions for the charge distribution and charge transfer on different transition states indicate that there are different molecular mechanisms for the different substituted ethenes. The calculations show that the effect of solvent decreases the activation energy and increases the asynchronicity. The results also indicate that the hydrogen-bond formation between chloroform and the carbonyl oxygen of the o-QM lowers the activation energies and increases the asynchronicity.