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Conjugate Addition vs Heck Reaction: A Theoretical Study on Competitive Coupling Catalyzed by Isoelectronic Metal (Pd(II) and Rh(I))
其他题名Pd2+ 和Rh+催化的共轭加成和Heck反应的理论研究
Peng Q(彭谦); Yan H(鄢红); Zhang XH(张新豪); Wu YD(吴云东)
2012
发表期刊J. Org. Chem.
ISSN0022-3263
卷号77期号:17页码:7487-7496
摘要Density functional theory studies have been carried out to investigate the mechanism of the Pd(II(bpy)-and Rh(I)(bpy)-catalyzed conjugate additions and their competitive Heck reactions involving alpha,beta-unsaturated carbonyl compounds. The critical steps of the mechanism are insertion and termination. The insertion step favors 1,2-addition of the vinyl-coordinated species to generate a stable C-bound enolate intermediate, which then may isomerize to either an oxa-pi-allyl species or an O-bound enolate. The termination step involves a competition between beta-hydride elimination, leading to a Heck reaction product, and protonolysis reaction that gives a conjugate addition product. These two pathways are competitive in the Pd(II)-catalyzed reaction, while a preference for protonolysis has been found in the Rh(I)-catalyzed reaction. The calculations are in good agreement with the experimental observations. The potential energy surface and the rate-determining step of the beta-hydride elimination are similar for bcth Pd(II)- and Rh(I)-catalyzed processes. The rate-determining steps of the Pd(II)- and Rh(I)-catalyzed protonolysis are different. Introduction of an N- or P-ligand significantly stabilizes the protonolysis transition state via the O-bound enolate or oxa-pi-allyl complex intermediate, resulting in a reduced free energy of activation. However, the barrier of the beta-hydride elimination is less sensitive to ligands. For the Rh(I)-catalyzed reaction, protonolysis is calculated to be more favorable than the beta-hydride elimination for all investigated N and P ligands due to the significant ligand stabilization to the protonolysis transition state. For the Pd(II)-catalyzed reaction, the complex with monodentate pyridine ligands prefers the Heck-type product through beta-hydride elimination, while the complex with bidentate N and P ligands favors the protonolysis. The theoretical finding suggests the possibility to control the selectivity between the conjugate addition and the Heck reaction by using proper ligands.
学科领域金属有机化学
部门归属中科院上海有机化学研究所; 香港科技大学
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收录类别SCI
语种英语
WOS记录号WOS:000308390100030
引用统计
被引频次:31[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://ir.sioc.ac.cn/handle/331003/28161
专题金属有机化学国家重点实验室
通讯作者Wu YD(吴云东)
推荐引用方式
GB/T 7714
Peng Q,Yan H,Zhang XH,et al. Conjugate Addition vs Heck Reaction: A Theoretical Study on Competitive Coupling Catalyzed by Isoelectronic Metal (Pd(II) and Rh(I))[J]. J. Org. Chem.,2012,77(17):7487-7496.
APA 彭谦,鄢红,张新豪,&吴云东.(2012).Conjugate Addition vs Heck Reaction: A Theoretical Study on Competitive Coupling Catalyzed by Isoelectronic Metal (Pd(II) and Rh(I)).J. Org. Chem.,77(17),7487-7496.
MLA 彭谦,et al."Conjugate Addition vs Heck Reaction: A Theoretical Study on Competitive Coupling Catalyzed by Isoelectronic Metal (Pd(II) and Rh(I))".J. Org. Chem. 77.17(2012):7487-7496.
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