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Synthesis And Catalytic Performance Of Supported Chiral Ruthenium And Olefin Metathesis Reaction Catalyst

Posted on:2022-07-17Degree:MasterType:Thesis
Country:ChinaCandidate:X Y LiFull Text:PDF
GTID:2491306725453144Subject:Chemical Biology
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With the increasing demand for catalysts in chemical research,homogeneous metal ruthenium catalysts have been unable to adapt to the development of chemical research.Homogeneous catalysts have shortcomings such as low reusability,difficulty in recycling,and instability.In order to improve the stability and reusability of the catalyst,this topic will modify the homogeneous ruthenium catalyst to achieve higher reusability and stability.This subject will use Grubbs-Hoveyda 2nd ruthenium catalyst as the core structure for research.There are three main research sites:the first type is anionic ligands,which are mainly divided into ionic liquid-containing silver carboxylate ligands and amino acid silver ligands;One is Hoveyda chelating ligand,which is mainly to form an ionic compound supported by a solid;the third is a nitrogen-containing heterocyclic carbene ligand,which mainly synthesizes two non-polar aromatic ring substituents.Ligand and two internal salt type(one is biphenol,the other is benzenesulfonate)nitrogen-containing heterocyclic ligands.Research on homogeneous catalysts found that the L-type amino acid catalyst 2-12a-L has higher stereoselectivity than the D-type amino acid catalyst 2-12a-D in the ARCM reaction catalyzed by the ee value increased by 6%;the cumene substituted The ee value of the ARCM reaction catalyzed by the catalyst 2-10b for the synthesis of nitrogen-containing heterocyclic rings is significantly higher than that of the catalyst 2-10a for the synthesis of nitrogen-containing heterocyclic rings which are substituted by trimethyl,and the ee value is increased by 26%.For the research of Hoveyda ligand,four supported metal ruthenium catalysts were successfully synthesized.The ARCM reaction catalyzed by the magnetic supported catalyst 3-19a,when the product is 3-30b,the yield is>98%,and the ee value is 37%.When catalyzing the AROCM reaction,the ee value of the product 3-35b is the highest(23%),and E/Z=1.0:1.0;the ee value of the product 3-33b is 20%,and the product only has the E configuration.Using3-29b as a substrate,the catalyst 3-19a was used repeatedly,and the results showed that the yields were all above 90%when used repeatedly for 9 times;the yields were all above 80%when used repeatedly for 13 times.The catalyst 3-19a and the catalyzed product 3-38b have high antibacterial activity against Curvularia lunata,with an IC50 value of 46.66 ug/mL.This project adopts the method of magnetic carrier to solve the problem of catalyst activity and metal separation,and improves the stability of the catalyst and increases the number of repeated uses of the catalyst.The supported catalyst has the advantages of being recoverable and recyclable,and effectively reducing the pollution of metal ruthenium.
Keywords/Search Tags:magnetic nanoparticles, ruthenium, chiral metal catalysts, immobilization, olefin metathesis reaction
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