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THE APPLICATION OF SPIROLIGOMERS TOWARDS MOLECULAR RECOGNITION AND ORGANOCATALYSISFan, Yanfeng January 2019 (has links)
This thesis presents the development of bis-amino acid-based spiroligomer applications in the areas of molecular recognition and organocatalysis. By taking advantage of the high degree of functionality and chirality of the unique bis-amino acid building blocks, spiroligomer backbones can be synthesized with predefined shapes, functioning as molecular hosts or as enzyme active-site-like pockets. Firstly, we demonstrated that spiroligomers can be designed to act as anion receptors. We designed a collection of spiroligomers that each display two urea groups. The spiroligomer that displayed the two urea groups in a way that they pointed at each other acts as an anion receptor and binds hydrogen pyrophosphate H2PPi anion (H2P2O72−), as demonstrated by an NMR titration experiment. Other spiroligomers that displayed the two ureas demonstrated a variety of behaviors including self-association and gel formation. In later work we explored the use of spiroligomers to develop catalysts. We attempted to design bipyridine/TEMPO-based bifunctional catalysts but they failed to achieve a faster alcohol oxidation rate than the background reaction. We then demonstrated the successful incorporation of metal-salen functional groups into spiroligomers in Chapter 4. Several bis-amino acid-based metal-salen complexes were synthesized and examined as asymmetric catalysts. Although only moderate enantio-selectivity was detected from synthesized Mn-salen catalyzed epoxidation reactions, it provides the first direct evidence that chiral bis-amino acid backbone can act as a chiral pocket that influence substrate selection and the stereochemical outcome of reactions. / Chemistry
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Développement d'une méthode d'alkylation pour la préparation de ligands carbènes N-hétérocycliques C₁-symétriques et synthèse de nouveaux catalyseurs pour la métathèse d'oléfinesSavoie, Jolaine January 2008 (has links)
Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.
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Développement d'une méthode d'alkylation pour la préparation de ligands carbènes N-hétérocycliques C₁-symétriques et synthèse de nouveaux catalyseurs pour la métathèse d'oléfinesSavoie, Jolaine January 2008 (has links)
Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal
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