Z-Selectivity in Olefin Metathesis with Chelated Ru Catalysts: Computational Studies of Mechanism and Selectivity
Z-Selectivity in Olefin Metathesis with Chelated Ru Catalysts: Computational Studies of Mechanism and Selectivity
复制标题
螯合钌催化剂在烯烃复分解中的 Z 选择性：机理和选择性的计算研究
DOI：
10.1021/ja2108728
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发表时间：
2012-01-25
影响因子：
15
通讯作者：
Houk, K. N.
中科院分区：
文献类型：
--
作者：
Liu, Peng;Xu, Xiufang;Houk, K. N.
用密度泛函理论探讨了络合型Ru催化剂催化烯烃歧化反应中Z-选择性的机理和来源。与以前未螯合的Ru催化剂的反应倾向于底键路径相反，烯烃从螯合型Ru催化剂的“侧”位置靠近。烯烃上的取代基与N-杂环卡宾配体上的N-取代基之间的空间斥力导致Z产物的高度选择性形成。
The mechanism and origins of Z-selectivity in olefin metathesis with chelated Ru catalysts were explored using density functional theory. The olefin approaches from the "side" position of the chelated Ru catalysts, in contrast to reactions with previous unchelated Ru catalysts that favor the bottom-bound pathway. Steric repulsions between the substituents on the olefin and the N-substituent on the N-heterocyclic carbene ligand lead to highly selective formation of the Z product.