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Hétéroarylation et arylation des éthers d'énol par couplages directs catalytiques impliquant des liaisons C-CO² H et C-H

Abstract : To date, one of the challenges in the development of catalytic direct couplings of [CH / C-CO2H] and [CH / CH] type is the functionalization of molecules, with high synthetic value, having a high potential of development in the goal of increasing structural and functional diversity. Enol ethers are part of this class of structural motifs; however, till now, no economical and selective functionalization method have been developed. In this context, the aim of this work was to develop a selective (hetero)arylation strategy of α-carboxyvinyl ether by direct dehydrogenative CH/ CH or decarboxylative C-H / C-CO2H cross coupling using α-alkoxy cinnamics acid and α-etheroxyacrylates as coupling partners. The first chapter has been focused on the development of the first methodology for the preparation of gem-heteroaryl enol ethers based on the engagement of α-alkoxylated cinnamic acids in the direct coupling of [C-CO2H / C-H] type under cooperative Pd(0) / Cu(I) catalysis. This methodology gave access to the α-enolizable 2-ketoheteroarenes after modulation of the enol ether function, and these were then valorized to give the 2,4'-bis-azole systems that are present in the natural polypeptides. The second and third chapters have focused on the study of β-functionalization of enol ethers by direct and selective Pd-catalyzed coupling of ethyl α-etheroxyacrylates according to two strategies: (1) Myers’s type decarboxylative Heck coupling [C-H / C-CO2H] with benzoic acid derivative and (2) Fujiwara-Moritani’s type [C-H / C-H] oxidative coupling.
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Mahmoud Hachem. Hétéroarylation et arylation des éthers d'énol par couplages directs catalytiques impliquant des liaisons C-CO² H et C-H. Chimie organique. Normandie Université, 2019. Français. ⟨NNT : 2019NORMR128⟩. ⟨tel-02516000⟩

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