Jakoobi Martin, Dardun Vincent, Veyre Laurent, Meille Valérie, Camp Clément, Thieuleux Chloé
Université de Lyon, Institut de Chimie de Lyon, Laboratory of Chemistry, Catalysis, Polymers and Processes, C2P2 UMR 5265 CNRS-UCB Lyon 1-CPE Lyon, 43 Bd du 11 Novembre 1918, F-69616 Villeurbanne, France.
Université de Lyon, Institut de Chimie de Lyon, Laboratoire de Génie des Procédés Catalytiques, UMR 5285 CNRS-UCB Lyon 1-CPE Lyon, CPE Lyon, 43 Bd du 11 Novembre 1918, F-69616 Villeurbanne, France.
J Org Chem. 2020 Sep 18;85(18):11732-11740. doi: 10.1021/acs.joc.0c01439. Epub 2020 Sep 9.
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 (MDM). 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 MDM, 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.
这项工作描述了在溶液中制备易于制备的钴纳米颗粒（NPs）的过程，这些颗粒有望作为工业相关叔硅烷1,1,1,3,5,5,5-七甲基三硅氧烷（MDM）进行烯烃硅氢化反应的替代催化剂。在甲苯中于30°C使用3.5 - 7小时，催化剂负载量为0.05 - 0.2 mol%且无添加剂的情况下，钴纳米颗粒表现出高活性。在这些温和条件下，发现一系列末端烯烃与MDM反应，仅生成反马氏产物，产率高达99%。此外，我们证明了使用紫外线照射进一步活化这些钴纳米颗粒的可能性，这不仅能提高它们的催化性能，还能促进使用内烯烃（包括不饱和脂肪酸酯（油酸甲酯））的串联异构化 - 硅氢化反应，以高达定量产率生成线性产物。
