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Méthodologies de synthèse diastéréosélectives d'ortho-1,2-diaminoalkylphénols, vers la synthèse totale des bioxalomycines - réaction tandem de N-arylation / Heck compétitive.

Abstract : Inter- and intramolecular diastereoselective syntheses of ortho-1,2-diaminoalkylphenols, subunits found in the structure of bioxalomycins, cyanocyclins and naphthyridinomycin, are reported in this thesis. Intermolecular strategies: a new diastereodivergent three-component Mannich phenolic reaction, catalyzed by Lewis acids such as ytterbium triflate, is reported for the synthesis of chiral ortho-1,2-diaminoalkylphenols, from a phenol, a N,N-dibenzyl-alpha-amino aldehyde and an amine. Intramolecular strategies: a new intramolecular cyclization of bis-trichloroacetimidates from chiral 2-amino-1,3-diols, gives access to the trans-5-amino-4-aryl-5,6-dihydro-4H-1,3-oxazine subunit, by a SN1 mechanism. The application of this methodology to a more advanced tetrahydroisoquinoline type substrate allowed the access to a dihydrooxazine containing the syn vicinal diamine found in bioxalomycins. From the crystallization of a macrocyclic bis-sigma-arylpalladium complex involved in a intramolecular N-arylation / C-H activation / Caryl-Caryl coupling domino process developed at our laboratory for the synthesis of diazaphénanthrenes-benzodiazepinones, divergent conditions were found, based on a competitive Heck coupling. This new method leads to 3-(N-methylphenyl)acrylate benzodiazepinone subunit.
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Submitted on : Tuesday, July 27, 2010 - 3:53:49 PM
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Christophe Rondot. Méthodologies de synthèse diastéréosélectives d'ortho-1,2-diaminoalkylphénols, vers la synthèse totale des bioxalomycines - réaction tandem de N-arylation / Heck compétitive.. Génie chimique. Ecole Polytechnique X, 2005. Français. ⟨pastel-00001537⟩

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