Kinetic selectivity of olefin metathesis catalysts bearing cyclic (alkyl)(amino)carbenes
Kinetic selectivity of olefin metathesis catalysts bearing cyclic (alkyl)(amino)carbenes
复制标题
DOI：
10.1021/om7008028
复制
发表时间：
2008-02-25
期刊：
影响因子：
2.8
通讯作者：
Schrodi, Yann
中科院分区：
文献类型：
--
作者：
Anderson, Donde R.;Ung, Thay;Schrodi, Yann
本文报道了带有环（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）的交叉复分解反应和油酸甲酯（11）的乙烯醇分解反应中的评价。相对于大多数NHC取代的络合物，CAAC取代的催化剂在7和8的交叉复分解中表现出较低的E/Z比（在70%转化率下为3：1）。此外，配合物4-6在11的乙烯醇分解中表现出形成末端烯烃相对于内烯烃的良好选择性。事实上，复合体6达到了35000吨，是迄今为止的最高记录。CAAC取代的配合物表现出显着不同的动力学选择性比大多数NHC取代的配合物。
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.