Nitro-substituted Hoveyda-Grubbs ruthenium carbenes: Enhancement of catalyst activity through electronic activation

被引:415
作者
Michrowska, A
Bujok, R
Harutyunyan, S
Sashuk, V
Dolgonos, G
Grela, K
机构
[1] Polish Acad Sci, Inst Organ Chem, PL-01224 Warsaw, Poland
[2] Polish Acad Sci, Inst Phys Chem, PL-01224 Warsaw, Poland
关键词
D O I
10.1021/ja048794v
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The design, synthesis, stability, and catalytic activity of nitro-substituted Hoveyda-Grubbs metathesis catalysts are described. The highly active and stable meta- and para-substituted complexes are attractive from a practical point of view. These catalysts operate in very mild conditions and can be successfully applied in various types of metathesis [ring-closing metathesis, cross-metathesis (CM), and enyne metathesis]. Although the presence of a NO2 group leads to catalysts that are dramatically more active than both the second-generation Grubbs's catalyst and the phosphine-free Hoveyda's carbene, enhancement of reactivity is somewhat lower than that observed for a sterically activated Hoveyda-Grubbs catalyst. Attempts to combine two modes of activation, steric and electronic, result in severely decreasing a catalyst's stability. The present findings illustrate that different Ru catalysts turned out to be optimal for different applications. Whereas phosphine-free carbenes are catalysts of choice for CM of various electron-deficient substrates, they exhibit lower reactivity in the formation of tetrasubstituted double bonds. This demonstrates that no single catalyst outperforms all others in all possible applications.
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收藏
页码:9318 / 9325
页数:8
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