成果信息
Mechanisms and stereoselectivities of phosphine-catalyzed domino reaction of alpha-benzyl allenoate with 5-phenylmethylene thiazolone: a computational investigation
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文献类型:期刊论文
标题:Mechanisms and stereoselectivities of phosphine-catalyzed domino reaction of alpha-benzyl allenoate with 5-phenylmethylene thiazolone: a computational investigation
作者:Li, Yan[1];Fu, Wenwen[1];Liang, Changhai[1]
机构:
通讯作者:Li, Y (reprint author), Dalian Univ Technol, Sch Petr & Chem Engn, Panjin Campus, Dalian 124221, Peoples R China.
来源信息:年:2018  卷:137  期:1  
期刊信息:THEORETICAL CHEMISTRY ACCOUNTS影响因子和分区  ISSN:1432-881X
增刊:正刊
学科:化学
收录情况:SCIE(WOS:000417536800001)  
所属部门:盘锦校区石油与化学工程学院
语言:外文
发表时间:2018-12-07
全文链接:DOI百度学术
人气指数:811
浏览次数:811
基金:National Natural Science Foundation of China [21403024]; National Supercomputing Center in Shenzhen
关键词:[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.
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