Chem. J. Chinese Universities ›› 2010, Vol. 31 ›› Issue (1): 106.

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Theoretical Study on the Diels-Alder Reactions Between Germabenzenes and Dienophiles

WANG Yan1*, ZENG Xiao-Lan1, FANG De-Cai2   

  1. 1. College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang 464000, China;
    2. College of Chemistry, Beijing Normal University, Beijing 100875, China
  • Received:2009-03-17 Online:2010-01-10 Published:2010-01-10
  • Contact: WANG Yan. E-mail: wangyanxytc@163.com
  • Supported by:

    国家自然科学基金(批准号: 20773016)和河南省基础与前沿技术研究计划项目(批准号: 092300410207)资助.

Abstract:

Density functional theory(DFT) calculations, at the B3LYP/6-311G(d,p) level of theory, were performed to study the reaction mechanism and potential energy surface of the Diels-Alder reactions between germabenzenes and some dienophiles. The influences of substituents and benzene as a solvent on the potential energy surface of the hetero-Diels-Alder reactions were investigated and the origin of regioselectivity in the he-tero-Diels-Alder reactions was explored. Our calculation results show that all of studied reactions proceed in a concerted way. The influences of phenyl at C atom of dienophiles on the asynchronicity in the bond-formation process and activation barrier of reaction are closely related to the relative position of phenyl with respect to Ge atom in products. The CCl3 group at Ge atom of germabenzene molecule is in favor of process of the hetero-Diels-Alder reactions and solvent effect is not crucial for the potential energy surfaces of the studied reactions. The present calculations reproduce the regioselectivity observed experimentally in hetero-Diels-Alder reactions, which indicates that the kinetic factor controls the reaction proceeding.

Key words: Germabenzene; Dienophile; Diels-Alder reaction; Reaction mechanism; Density functional theory

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