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个人信息Personal Information
教授
博士生导师
硕士生导师
任职 : 大连理工大学成都研究院院长
性别：男
毕业院校：中科院大连化学物理研究所
学位：博士
所在单位：化工学院
学科：化学工艺. 物理化学. 功能材料化学与化工
办公地点：大连理工大学西部校区化工综合楼A401室
联系方式：辽宁省大连市高新区凌工路2号，邮编116024
电子邮箱：changhai@dlut.edu.cn
Mechanisms and stereoselectivities of phosphine-catalyzed domino reaction of alpha-benzyl allenoate with 5-phenylmethylene thiazolone: a computational investigation
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论文类型：期刊论文
发表时间：2018-12-07
发表刊物：THEORETICAL CHEMISTRY ACCOUNTS
收录刊物：SCIE
卷号：137
期号：1
ISSN号：1432-881X
关键字：[2+4] Cycloaddition; Density functional theory; Reaction mechanisms; Stereoselectivity
摘要：A computational examination of the phosphine-catalyzed domino reaction of alpha-benzyl allenoate with 5-phenylmethylene thiazolone has been carried out at the SMD(toluene)M06-2X/6-311+G(d,p)//M06-2X/6-31G(d) level. Various possible reaction pathways have been located and compared. Computations show that the preferred mechanism consists of four reaction steps: (I) the nucleophilic attack of phosphine catalyst to alpha-benzyl allenoate and generation of dienolate intermediate; (II) the nucleophilic conjugate addition to 5-phenylmethylene thiazolone; (III) the intramolecular cyclization, and (IV) the liberation of catalyst. The first step is the rate-determining step with an overall free energy barrier of 29.4 kcal/mol, and the second step is found to be the stereoselectivity-determining step. The predicted high enantioselectivities are in good agreement with the experimental observations. The present study should be useful for understanding this kind of reaction in the future.