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Ancrage supramoléculaire de complexes organométalliques dans la béta-lactoglobuline pour la catalyse asymétrique dans l'eau. Effet des ligands prochiraux hémilabiles.

Abstract : This PhD work focused on the development of artificial metalloenzymes. Such a concept allows to combine typical advantages of both enzymatic and organometallic catalysts, such as high catalytic selectivity and efficiency of enzymatic systems and wide substrate scope of transition metals catalysts. Our approach consists in the utilization of transition metal complexes with a prochiral hemilabile ligand, once embedded within the protein host, could be forced to adopt a specific stereoconfiguration. This would in turn make possible to bring the chirality centers closer to the catalytic metal center and, therefore, to increase the enantioselectivity of catalyzed reactions.In this thesis, we report the synthesis of new palladium complexes of prochiral hemilabile NCN pincer ligands and the study of their structural properties. Furthermore, the supramolecular anchoring of these complexes to bovine β-lactoglobulin (β-LG) was studied both experimentally and theorically by computational calculation. These constructs were shown to catalyze aldol condensation reactions in aqueous media, affording, in some cases, the less-favorable cis product. This unusual diastereoselectivity was ensued by the second sphere of coordination brought by the protein host. In a second part, the synthesis of new half sandwich ruthenium complexes of prochiral hemilabile β-aminothioether ligands is reported as well as the study of their insertion in the protein. The hybrids catalyzed the transfer hydrogenation of arylketones with high enantioselectivity. The enhancement of selectivity was attributed to chirality.
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https://tel.archives-ouvertes.fr/tel-01725138
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Submitted on : Wednesday, March 7, 2018 - 10:35:14 AM
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  • HAL Id : tel-01725138, version 1

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Lucrèce Pocquet. Ancrage supramoléculaire de complexes organométalliques dans la béta-lactoglobuline pour la catalyse asymétrique dans l'eau. Effet des ligands prochiraux hémilabiles.. Chimie analytique. Université Pierre et Marie Curie - Paris VI, 2017. Français. ⟨NNT : 2017PA066322⟩. ⟨tel-01725138⟩

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