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Etude de la réaction de Povarov : synthèse énantiosélective de composés diaminés organocatalysée par des acides phosphoriques chiraux

Abstract : This work deals with the Povarov reaction, an inverse electron-demanding Diels-Alder reaction between 2-aza-dienes (generally an N-aryl-imine) and a dienophile such as an electron-rich olefin, leading to the formation of tetrahydroquinolines. We were able to perform this reaction in a multicomponent way, ie by the in situ formation of the imine from the corresponding aldehyde and aniline. Moreover, this multicomponent reaction was also énantiosélective, by using chiral phosphoric acids as catalysts, and by choosing enecarbamates as diénophiles, which could interact with the catalyst thanks to their N-H bond. This methodology allowed to synthesize 4-amino-tetrahydroquinolines in good yields with total diastereoselectivities and excellent enantioselectivities. The use of ene-thioureas as dienophiles also allowed to synthesize hexahydropyrroloquinolines with the same selectivities, following the same method.We also studied the mechanism of this Povarov reaction. We proved that it is a stepwise mechanism, by trapping the iminium intermediate, either via an intermolecular reaction with ethanol leading to chiral 1,3-diamines, or via an intramolecular reaction in the particular case of phenylacetaldehyde, then leading to 1,3-diaminotetralins.
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Submitted on : Wednesday, March 20, 2013 - 1:35:25 PM
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  • HAL Id : tel-00802712, version 1

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Guillaume Dagousset. Etude de la réaction de Povarov : synthèse énantiosélective de composés diaminés organocatalysée par des acides phosphoriques chiraux. Autre. Université Paris Sud - Paris XI, 2011. Français. ⟨NNT : 2011PA112274⟩. ⟨tel-00802712⟩

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