含环状（烷基）（氨基）卡宾的烯烃复分解催化剂的动力学选择性
Kinetic Selectivity of Olefin Metathesis Catalysts Bearing Cyclic (Alkyl)(Amino)Carbenes.
作者信息
Anderson Donde R, Ung Thay, Mkrtumyan Garik, Bertrand Guy, Grubbs Robert H, Schrodi Yann
机构信息
The Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125.
出版信息
Organometallics. 2008 Jan 12;27(4):563-566. doi: 10.1021/om7008028.
The evaluation of ruthenium olefin metathesis catalysts 4-6 bearing cyclic (alkyl)(amino)carbenes (CAACs) in the cross-metathesis of cis-1,4-diacetoxy-2-butene (7) with allylbenzene (8) and the ethenolysis of methyl oleate (11) is reported. Relative to most NHC-substituted complexes, CAAC-substituted catalysts exhibit lower E/Z ratios (3:1 at 70% conversion) in the cross-metathesis of 7 and 8. Additionally, complexes 4-6 demonstrate good selectivity for the formation of terminal olefins versus internal olefins in the ethenolysis of 11. Indeed, complex 6 achieved 35 000 TONs, the highest recorded to date. CAAC-substituted complexes exhibit markedly different kinetic selectivity than most NHC-substituted complexes.
报道了带有环状（烷基）（氨基）卡宾（CAAC）的钌烯烃复分解催化剂4 - 6在顺式-1,4 - 二乙酰氧基-2 - 丁烯（7）与烯丙基苯（8）的交叉复分解反应以及油酸甲酯（11）的乙烯解反应中的评估情况。相对于大多数N - 杂环卡宾取代的配合物，CAAC取代的催化剂在7和8的交叉复分解反应中表现出较低的E/Z比（70%转化率时为3:1）。此外，配合物4 - 6在11的乙烯解反应中对末端烯烃与内烯烃的形成表现出良好的选择性。实际上，配合物6实现了35000的TON值，这是迄今为止记录到的最高值。CAAC取代的配合物表现出与大多数N - 杂环卡宾取代的配合物明显不同的动力学选择性。
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