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Developing a Highly Active Catalytic System Based on Cobalt Nanoparticles for Terminal and Internal Alkene Hydrosilylation.
The Journal of Organic Chemistry ( IF 3.6 ) Pub Date : 2020-08-26 , DOI: 10.1021/acs.joc.0c01439
Martin Jakoobi 1 , Vincent Dardun 1 , Laurent Veyre 1 , Valérie Meille 2 , Clément Camp 1 , Chloé Thieuleux 1
Affiliation  

This work describes the development of easy-to-prepare cobalt nanoparticles (NPs) in solution as promising alternative catalysts for alkene hydrosilylation with the industrially relevant tertiary silane 1,1,1,3,5,5,5-heptamethyltrisiloxane (MDHM). The Co NPs demonstrated high activity when used at 30 °C for 3.5–7 h in toluene, with catalyst loadings 0.05–0.2 mol %, without additives. Under these mild conditions, a set of terminal alkenes were found to react with MDHM, yielding exclusively the anti-Markovnikov product in up to 99% yields. Additionally, we demonstrated the possibility of using UV irradiation to further activate these cobalt NPs not only to enhance their catalytic performances but also to promote tandem isomerization–hydrosilylation reactions using internal alkenes, among them unsaturated fatty ester (methyl oleate), to produce linear products in up to quantitative yields.

中文翻译:

开发基于钴纳米粒子的高活性催化体系,用于末端和内部烯烃氢化硅烷化。

这项工作描述了易于制备的钴纳米颗粒(NPs)在溶液中的发展,作为与工业相关的叔硅烷1,1,1,3,5,5,5,5-七甲基三硅氧烷(MD H M )。当在30°C的甲苯中使用3.5到7 h时,Co NPs表现出高活性,催化剂负载量为0.05-0.2 mol%,不含添加剂。在这些温和条件下,发现一组末端烯烃与MD H反应M,仅以高达99%的产率生产抗马氏蛋白产物。此外,我们证明了使用紫外线辐照进一步活化这些钴纳米颗粒的可能性,不仅可以增强它们的催化性能,而且还可以使用内部烯烃(其中包括不饱和脂肪酸酯(油酸甲酯))促进串联异构化-氢化硅烷化反应,从而生成线性产物达到定量产量。
更新日期:2020-09-20
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