Department of Chemistry, Technical University of Denmark, Building 201, Kemitorvet, DK-2800 Kgs. Lyngby, Denmark.
Chemistry. 2010 Aug 16;16(31):9494-501. doi: 10.1002/chem.201001158.
The mechanism of the recently developed palladium-catalyzed ene-yne coupling has been evaluated by DFT methods. The calculations validate the previously proposed reaction mechanism and explain the stereoselectivity of the reaction (exclusive formation of the E isomer of the disubstituted alkene). Concerning chemoselectivity, the calculations also clarify why the ene-yne coupling is able to dominate over plausible alternative reaction pathways such as alkene homocoupling and alkyne polymerization. The role of the phosphine ligand at various stages of the catalytic cycle has also been delineated.
通过 DFT 方法评估了最近开发的钯催化烯-炔偶联反应的机理。这些计算验证了先前提出的反应机理，并解释了反应的立体选择性（仅形成取代的烯烃的 E 异构体）。关于化学选择性，计算还阐明了为什么烯-炔偶联能够胜过可能的替代反应途径，如烯烃自身偶联和炔烃聚合。还描绘了膦配体在催化循环的各个阶段的作用。
