SIOC English
化学学报
高级检索

化学学报 ›› 2006, Vol. 64 ›› Issue (13): 1367-1372. 上一篇    下一篇

研究论文

钯含氮配合物催化烯烃芳基化反应的密度泛函研究

吕文阳，李明*，申伟，罗小玲，翟巧玲，黄浩   

  1. (西南师范大学化学系 重庆 400715)
  • 投稿日期:2005-07-22 修回日期:2006-03-07 发布日期:2006-07-14
  • 通讯作者: 李明

Density Functional Studies on Arylation of Alkene Catalyzed by Palladium(II)-Complex Including Nitrogen

LÜ Wen-Yang, LI Ming*, SHEN Wei, LUO Xiao-Ling, ZHAI Qiao-Ling, HUANG Hao   

  1. (Department of Chemistry, Southwest-China Normal University, Chongqing 400715)
  • Received:2005-07-22 Revised:2006-03-07 Published:2006-07-14
  • Contact: LI Ming

PDF

610

用密度泛函方法(DFT)研究了Pd(II)含氮配合物催化烯烃芳基化反应的机理. 结果表明, 该反应是放热的, 主要经历了对甲苯基对烯烃的迁移插入和β-H的还原消去. 对甲苯基对烯烃的迁移插入是反应的速率控制步骤和手性控制步骤. 理论预测的产物是与实验一致的(R)-2-甲基-2-苯基环戊酮.

关键词: 烯烃的芳基化, Pd(II)催化剂, 不对称催化, DFT, 反应机理

The mechanism of arylation of alkene catalyzed by palladium(II)-complex including nitrogen was studied by means of the density functional theory. As shown, this reaction was exothermic and went through the insertion of aryl and the reductive elimination of β-H. The insertion of aryl was the rate-determinating and the chirality-controlling step for this reaction. The dominant product predicted theoretically was R-2-methyl-2-phenyl cyclopentanone that was in agreement with the experiment.

Key words: arylation of alkene, palladium(II)-catalyst, asymmetric catalysis, density functional theory, reaction mechanism