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Réduction de difluorocyclopropènes par transfert d'hydrogène. Synthèse de difluorocyclopropanes optiquement enrichis

Abstract : Gem-Difluorocyclopropanes are encountered in bioactive compounds and are eliciting anincreasing interest in medicinal chemistry. Diastereoselective reactions, controlled by the substrateor chiral auxiliaries, as well as enzymatic reactions have classically been used to access enantioenriched gem-difluorocyclopropanes. Therefore, devising enantioselective catalytic synthetic methods toward functionalized gem-difluorocyclopropanes constitutes a major challenge. In this context, our work has been devoted to the development of an enantioselective conjugate reductionof gem-difluorocyclopropenyl esters which are readily accessible by the addition of difluorocarbene to alpha,bêta-unsaturated acetylenic esters. The conjugate reduction of gem-difluorocyclopropenoates was achieved by transfer hydrogenation, using isopropanol as donor, catalyzed by an(arene)ruthenium(II) complex possessing N-tosyl-1,2-diphenylethylenediamine as a chiral ligand.Optically enriched cis-disubstituted gem-difluorocyclopropyl esters were obtained with a very goodcontrol of both the diastereoselectivity and the enantioselectivity. The interest of the resulting gem-difluorocyclopropyl esters was highlighted through different post-functionalization reactions enabling access to a wide variety of carbonyl compounds, alcohols, amines and nitrogen heterocycles incorporating the gem-difluorocyclopropyl unit.
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Khalil Yamani. Réduction de difluorocyclopropènes par transfert d'hydrogène. Synthèse de difluorocyclopropanes optiquement enrichis. Chimie organique. Université Paris sciences et lettres, 2020. Français. ⟨NNT : 2020UPSLS024⟩. ⟨tel-03150586⟩

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