钯含氮配合物催化烯烃芳基化反应的密度泛函研究  

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

作　　者：吕文阳[1] 李明[1] 申伟[1] 罗小玲[1] 翟巧玲[1] 黄浩[1] 

机构地区：[1]西南师范大学化学系,重庆400715

出　　处：《化学学报》2006年第13期1367-1372,共6页Acta Chimica Sinica

基　　金：教育部重点科学技术(No.104263)资助项目.

摘　　要：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.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.

关 键 词：烯烃的芳基化 Pd(Ⅱ)催化剂 不对称催化 DFF 反应机理 

分 类 号：O643.32[理学—物理化学]