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Synthèse sélective de N-hétérocycles carbonylés par multi-catalyse homogène et hétérogène

Abstract : The one-pot selective synthesis of 4-quinolones and indoxyls was achieved through a carbonylative Sonogashira coupling followed by cyclization. A study in homogeneous catalysis revealed that the nature of catalysts in presence controlled the selectivity toward each compounds. Whereas the first coupling step is palladium catalyzed, the cyclizations require organic nucleophilic species. Thus, 4-quinolones were obtained by one-pot multi-catalysis {[Pd]+amine} and indoxyls by one-pot tandem catalysis {[Pd]/phosphine}. The catalytic systems were heterogenized by functionalizing mesostructured SBA silicas. Two strategies were employed aiming at a control of the localization of the functionality. Different Pd complexes were integrated in the pores of the material by post-synthesis grafting or incorporated into the walls via direct synthesis. Different amines and a phosphine were immobilized by post-synthesis grafting affording hybrid materials containing amine or phosphine catalysts in their pores. Catalytic activities of those materials were evaluated in the reaction affording 2-phenyl-4-quinolone and 2-benzylidene-indoxyl. The former was obtained in good yields and the heterogeneous catalytic system {[Pd]@SBA+amine@SBA} was recyclable over 3 runs. All hybrid materials showed Pd leaching but their uses still enables to decrease the Pd contamination of the final product compared to homogeneous complexes. The indoxyle compound was obtained in a semi-heterogeneous system {[Pd]@SBA/PPh3}, the use of the grafted phosphine providing transformation of the indoxyle toward 2-benzylindole. Formation of α-keto-amids by heterogeneously catalyzed double carbonylation was also studied
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Marie Genelot. Synthèse sélective de N-hétérocycles carbonylés par multi-catalyse homogène et hétérogène. Autre. Université Claude Bernard - Lyon I, 2011. Français. ⟨NNT : 2011LYO10003⟩. ⟨tel-00874806⟩

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