Date of Award
Master of Science
Levi M. Stanley
In this thesis, heterogeneous frameworks are explored and examined for their use in recyclable catalysis. Specifically, metal-organic-frameworks (MOFs) and covalent-organic-frameworks (COFs) containing bidentate nitrogen ligands are pursued for their use in transition metal catalysis.
Palladium(II)-functionalized COF (Pd@TpBpy COF) is demonstrated as a recyclable, heterogeneous catalyst for palladium-catalyzed conjugate addition of arylboronic acids to β,β-disubstituted enones to form ketone products containing all-carbon quaternary centers in aqueous 50 mM NaTFA as the reaction medium. A wide range of arylboronic acids are added to various β,β-disubstituted enones in moderate-to-high yields.
Pyridine oxazoline derivatives are designed and synthesized for incorporation into MOFs through varying methods including amide coupling, amine coupling, and solvent-assisted ligand incorporation (SALI). Preliminary data shows potential for palladium-catalyzed, enantioselective conjugate addition of phenylboronic acid to β,β-disubstituted enones to form ketone products.
Schumacher, Brian, "Design and application of porous organic frameworks for recyclable, heterogeneous, transition-metal catalysis" (2018). Graduate Theses and Dissertations. 16774.