A mechanistic study on multifunctional Fei-Phos ligand-controlled asymmetric palladium-catalyzed allylic substitutions
A mechanistic study on multifunctional Fei-Phos ligand-controlled asymmetric palladium-catalyzed allylic substitutions
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DOI：
10.1039/c6ra15665g
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发表时间：
2016-07
期刊：
影响因子：
3.9
通讯作者：
Jian‐Xing Xu;F. Ye;X. Bai;Yu-Ming Cui;Zheng Xu;Zhanjiang Zheng;Li‐Wen Xu
中科院分区：
文献类型：
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作者：
Jian‐Xing Xu;F. Ye;X. Bai;Yu-Ming Cui;Zheng Xu;Zhanjiang Zheng;Li‐Wen Xu
为了揭示Fei-Phos配体（手性反式-1，2-二氨基环己烷衍生的双膦，CycloN 2 P2-Phos）作为有效的手性P-配体存在下钯催化的烯丙基取代反应的机理，进行了机理研究以澄清多官能Fei-Phos在该反应中的作用。在钯催化的烯丙基烷基化反应中，氮磷原子的协同作用是一个双膦催化体系，而不是一个氮控制或单膦参与的过渡态。
To shield light on the mechanism of palladium-catalyzed allylic substitutions with structurally diverse nucleophiles (up to 99% ee) in the presence of Fei-Phos ligand (chiral trans-1,2-diaminocyclohexane-derived biphosphine, CycloN2P2-Phos) as an effective chiral P-ligand, mechanistic studies were performed for clarification of the role of multifunctional Fei-Phos in this reaction. The cooperative action of nitrogen and phosphorous atoms in the present Pd-catalyzed allylic alkylation is proved to be a diphosphine-based catalyst system but not a nitrogen-controlled or monophosphine-involved transition state.