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Novel Hydrogen Bonding Organocatalysts: Applications in the aza-Morita-Baylis-Hillman Reaction and Anion SensingDiep, Jenny 22 November 2013 (has links)
Self-assembly is an efficient method for generating large numbers of structurally diverse catalysts for screening. In this work, the method of self-assembly was explored in the construction of bifunctional catalysts, from a chiral aminophosphine, 2-formylphenylboronic acid, and a (thio)urea-containing diol. These catalysts were evaluated by their effect on the asymmetric aza-Morita-Baylis-Hillman reaction. In the second half of this thesis, the hydrogen bonding abilities of different dithiosquaramides were analyzed. As thioureas have been shown to be stronger hydrogen bond donors than ureas, it was hypothesized that dithiosquaramides may also follow a similar trend. Affinities of corresponding squaramides and dithiosquaramides to chloride, sulfate, and tosylate were compared, as well as their abilities to catalyze the Freidel-Crafts alkylation between indole and trans-β-nitrostyrene.
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Novel Hydrogen Bonding Organocatalysts: Applications in the aza-Morita-Baylis-Hillman Reaction and Anion SensingDiep, Jenny 22 November 2013 (has links)
Self-assembly is an efficient method for generating large numbers of structurally diverse catalysts for screening. In this work, the method of self-assembly was explored in the construction of bifunctional catalysts, from a chiral aminophosphine, 2-formylphenylboronic acid, and a (thio)urea-containing diol. These catalysts were evaluated by their effect on the asymmetric aza-Morita-Baylis-Hillman reaction. In the second half of this thesis, the hydrogen bonding abilities of different dithiosquaramides were analyzed. As thioureas have been shown to be stronger hydrogen bond donors than ureas, it was hypothesized that dithiosquaramides may also follow a similar trend. Affinities of corresponding squaramides and dithiosquaramides to chloride, sulfate, and tosylate were compared, as well as their abilities to catalyze the Freidel-Crafts alkylation between indole and trans-β-nitrostyrene.
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New developments in green asymmetric catalysis : Application to Michael reaction and ring opening polymerisation / Nouveaux développements en catalyse asymétrique verte : application à la réaction de Michael et à la polymérisation par ouverture de cycleChen, Li 18 July 2016 (has links)
La synthèse asymétrique organo-catalysée est un domaine de recherche en pleine expansion visant une chimie plus verte. Nous nous sommes intéressés au développement d’une réaction de Michael asymétrique organocatalysée en mettant à profit la catalyse par liaison hydrogène et l’activation énamine afin de contrôler en une seule étape la formation d’adduits portant un centre carboné quaternaire à partir de cétones non activées. Ainsi, nous avons développé des organocatalyseurs bifonctionnels de type squaramide qui ont permis d’obtenir les adduits de Michael attendu à partir de cycloalcanones alpha-substituées avec une bonne énantiosélectivité et une grande régiosélectivité dans un processus sous micro-ondes et sans solvant. Nous avons développé de nouveaux systèmes catalytiques sur la base du motif squaramide qui sont simples, efficaces et opérationnels. Nous avons étudié également l'utilité de nos systèmes organocatalytiques dans d'autres transformations comme la polymérisation verte. Afin de réduire l'utilisation de métaux toxiques pour produire des polymères bien définis sans trace de métaux et d'importance environnementale ou médicale, nous avons également étudié comment nos organo-catalyseurs de type squaramide pourraient contrôler la polymérisation verte par ouverture de cycle. Les systèmes organocatalytiques basés sur des squaramides étaient également applicables à la polymerisation par ouverture de cycle afin de donner des polylactides de dispersité étroite et de masses moléculaires contrôlées. / Organocatalyzed asymmetric synthesis is a growing and rapidly expanding research field for a greener chemistry. In this respect, we were interested in developing an organocatalyzed asymmetric Michael reaction taking advantage of H-bond catalysis and enamine activation allowing control of quaternary carbon center from unactivated ketones. Hence compared with well-known H-bond donor urea and thiourea organocatalysts, we first propose bifunctional squaramide organocatalysts for the one-pot transformation of unsymmetrical ketones to produce Michael adducts exhibiting a stereocontrolled quaternary carbon center in a neat microwave process. We also developped new catalytic systems based on the squaramide motive that are efficient and operationnaly simple, and produce Michael adducts in a good regioselectivity with an excellent enantio-selectivity. We also studied the usefulness of our systems in other transformations like green polymerization. In order to reduce the use of toxic metals to produce metal-free and well-defined polymers of environmental and medical significance, we also studied how our squaramide organocatalysts could control the green ring opening polymerization (ROP.The squaramide organocatalyst-based systems were also applicable to ROP to give polylactides of narrow dispersity and controlled molecular masses.
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