REACTIVITE DES NITRONES CYCLIQUES À SIX CHAINONS DERIVEES DE SUCRES VIS-A-VIS DE SmI 2 ET DE REACTIFS NUCLEOPHILES. SYNTHESE D'IMINOSUCRES

Abstract : Four new ketonitrones have been synthesized from D-fructose and L-sorbose. The ketone function of protected sugars has been transformed in oxime, then nitrones have been obtained by oxime N-alkylation / nucleophilic substitution of a well leaving group (in C-6 position) by nitrogen atom. Nitrones can be reduced by SmI2, reversing their polarity. A lot of nitrogen compounds can be obtained by their reductive cross-coupling with ketones, aldehydes or α,β-unsaturated esters. D-fructose or L-sorbose-derived nitrones have shown a different reactivity. After the SmI2 mediated reduction, the elimination of the alcoxy group was very fast. An original samarium (III) oxy-enamine intermediate has trapped a proton to furnish corresponding nitrones with an excellent yield. We have studied this new aspect of nitrones reactivity by trapping carbonyl compounds, to conduce to β-alkylated nitrones. Original N-hydroxylamines and amines have been obtained by reaction of this nitrones with allylmagnesium bromide and hydride. In another part, D-fructose or L-sorbose-derived nitrones have been transformed in polyhydroxylated piperidines and their N-oxygenated derivatives. Their ability to inhibit glycosidases or bacterian adhesion has been evaluated on various enzymes and lectin PA-IIL from Pseudomonas aeruginosa.
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Emilie Racine. REACTIVITE DES NITRONES CYCLIQUES À SIX CHAINONS DERIVEES DE SUCRES VIS-A-VIS DE SmI 2 ET DE REACTIFS NUCLEOPHILES. SYNTHESE D'IMINOSUCRES. Chimie organique. Université Joseph Fourier, Grenoble, 2009. Français. ⟨tel-01334316⟩

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