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MESOPOROUS SILICA MATERIALS IN ASYMMETRIC CATALYSIS AND SELECTIVE FUNCTIONALIZATIONSeki, Tomohiro 26 February 2013 (has links)
This thesis describes the synthesis and application of three types of selectively functionalized mesoporous materials. In the first section, periodically ordered mesoporous organosilicas (PMOs) are prepared that have the axially chiral bidentate phosphine ligand 2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) embedded in the wall structure. Asymmetric hydrogenation of β-ketoesters under high-pressure hydrogen gas and hydrogen transfer reduction were carried out using Ru catalysts resulting from these materials. In the next chapter, our new methodology to selectively functionalize the internal/external surface of SBA-15, a mesoporous silica whose pore diameter is ~8 nm, by blocking the pore surface with reloaded Pluronic P123® micelles is presented. Multiple tests were attempted to validate the efficiency of the methodology including nitrogen adsorption, quantitative analysis by solid state NMRs, fluorescence measurements, elemental analysis and XPS. Eventually SS NMR proved to be the most appropriate. Finally, chapter four describes ordered organic materials in catalysis, namely star-shaped polymers containing chiral core-gels synthesized from chiral 1,1’- binaphthalene-2,2’-diol (BINOL) and 1,1’-binaphthalene-2,2’-diamine (BINAM). The kinetic resolution of 1-phenyl ethanol was carried out expecting to see differential affinity of the chiral core-gel to one enantiomer of the substrate in hydrogen transfer oxidation reaction. / Thesis (Ph.D, Chemistry) -- Queen's University, 2013-02-25 12:08:40.27
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