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<dc:title xml:lang="fr">Capsules à base de résorcin[4]arène : synthèse, formation de complexes d’inclusion et effet en catalyse homogène</dc:title>
<dcterms:alternative xml:lang="en">Resorcin[4]arene-based capsules : inclusion complex formation, and effects in homogeneous catalysis</dcterms:alternative>
<dc:subject xml:lang="fr">Catalyse en espace confiné</dc:subject>
<dc:subject xml:lang="fr">Résorcinarènes</dc:subject>
<dc:subject xml:lang="fr">Capsules supramoléculaires</dc:subject>
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<dc:subject xml:lang="fr">Organocatalyse</dc:subject>
<dc:subject xml:lang="en">Confined spaces catalysis</dc:subject>
<dc:subject xml:lang="en">Resorcinarenes</dc:subject>
<dc:subject xml:lang="en">Supramolecular capsules</dc:subject>
<dc:subject xml:lang="en">Metal complexes</dc:subject>
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<dcterms:abstract xml:lang="fr">Ce manuscrit porte sur la catalyse homogène en espace confiné au sein d’entités résorcin[4]arènes. Trois axes ont été explorés : i) l’encapsulation de complexes métalliques, neutres ou cationiques, dans la capsule d’Atwood. Ces complexes d’inclusion, à base de ruthénium, de rhodium ou de palladium, ont été mis à profit en catalyse (oxydation, hydrosilylation, hydrogénation, cycloaddition, dimérisation). La seconde sphère de coordination apportée par la capsule supramoléculaire permet une modulation de l’activité, de la régiosélectivité ainsi qu’une discrimination des substrats ; ii) l’organocatalyse grâce à la capsule d’Atwood, illustrée par deux exemples : l’hydrogénation d’alcynes en présence d’un ammonium servant de co-catalyseur, et la formation d’indigoïdes à partir d’indoles ; iii) la synthèse de nouveaux assemblages capsulaires, incluant une pallado-capsule favorisant l’hydrogénation au détriment de l’hydrosilylation d’alcynes, et deux capsules dimériques, liées par des liaisons hydrogène, dont l’une est active en hydrolyse de phosphite, et la seconde montre un réarrangement sensible à la nature du solvant (CHCl3 contre CH2Cl2).</dcterms:abstract>
<dcterms:abstract xml:lang="en">This manuscript focuses on homogeneous confined spaces catalysis within resorcin[4]arenyl moieties. Three main areas have been explored: i) the encapsulation of metal complexes, either neutral or cationic, within the Atwood capsule. These inclusion complexes, based on ruthenium, rhodium, or palladium, have been used in catalysis (oxidation, hydrosilylation, hydrogenation, cycloaddition, dimerization). The secondary coordination sphere provided by the supramolecular capsule enables modulation of activity, regioselectivity, and substrate discrimination; ii) organocatalysis using the Atwood capsule, illustrated by two examples: the hydrogenation of alkynes in the presence of an ammonium co-catalyst, and the formation of indigoid compounds from indoles; iii) the synthesis of new capsular assemblies, including a palladium-based capsule favoring hydrogenation over hydrosilylation of alkynes, and two dimeric capsules connected by hydrogen bonds, one active in phosphite hydrolysis, and the other exhibiting a rearrangement sensitive to the nature of the solvent (CHCl3 versus CH2Cl2).</dcterms:abstract>
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