DFT studies on the mechanism of Pd(II)-catalyzed intermolecular 1,2-diamination of conjugated dienes

被引:3
作者
Yu, Youqing [1 ]
Shen, Wei [1 ]
Zhang, Jinsheng [1 ]
He, Rongxing [1 ]
Li, Ming [1 ]
机构
[1] Southwest Univ, Dept Chem, Chongqing 400715, Peoples R China
关键词
Pd(II)-catalyzed; DFT; diamination reaction; reaction mechanism;
D O I
10.1002/poc.1409
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The reaction mechanism of the palladium(II)-catalyzed addition of urea to dienes to form 1,2-diamine was studied using the B3LYP density functional theory (DFT) method. The results indicate that the first C-N sigma-bond formation is the rate-determining step, and that the covalent bonds are formed favorably by the terminal carbon atoms of dienes and nitrogen atom. The Pd(NCMe)-catalyst may significantly lower the energy barrier of the rate-determining step from the nonligand Pd(II)-catalyst counterpart. The results are in strong support of a recent experiment. Copyright (C) 2008 John Wiley & Sons, Ltd.
引用
收藏
页码:979 / 987
页数:9
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