Engineered Multifunctional Mesoporous Silica Materials for Cooperative and Cascade Catalysis

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CLEVELAND-DISSERTATION-2021.pdf (5.82 MB)
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Cleveland, Jacob William
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School of Chemical and Biomolecular Engineering
School established in 1901 as the School of Chemical Engineering; in 2003, renamed School of Chemical and Biomolecular Engineering
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http://hdl.handle.net/1853/70059
Abstract
Cascade catalysis is the process where multiple synthetic transformations are catalyzed in a one-pot procedure. Cooperatively catalyzed reactions are those where multiple catalyst structures work to offer enhanced rates when compared to the use of a single catalyst. The heterogenization of molecular catalysts has enabled a wide breadth of works in the fields of cascade and cooperative catalysis over the past 20 years. This thesis aims seeks novel approaches to develop multicatalytic materials for the purposes for cooperative and cascade reactions by using polymer and silica supported molecular catalysts. In the first work, a modular approach for the compartmentalization of mutually incompatible supported acids and bases is investigated using polymer molecular weight and mesopore size in several composite catalysts. It was found that lower molecular weight composite systems result in the most effective compartmentalization and activity during a deacetalization – Knoevenagel condensation sequence. In the second thesis aim, cooperativity between basic polymer supported benzylamines and weakly acidic silica silanols is engineered during the aldol condensation reaction. Low molecular weight systems outperform higher molecular weight and polymer-free analogues, and copolymer composition plays little to no role during this reaction. In the third project, a novel bifunctional catalyst is developed for a three-step application-based cascade from commodity chemical for the production of a biologically interesting compound. This is accomplished using supported tertiary amine (dimethylaminopropyl) and tetramethylpiperidine nitroxide radical (TEMPO) catalysts. Starting with benzyl alcohol, over 80% yield of the final product (chromene) is accomplished in 26 h.
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2022-05-05
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