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Conception en milieu superacide de dications chiraux pour la synthèse de composés fluorés et/ou hétérocycliques azotés

Abstract : Thanks to their exceptional acidity, superacid allow access to polycationic superelectrophiles by polyprotonation. These highly reactive species are capable of being trapped by very weak nucleophiles and can be used to develop new synthetic methodologies that do not exist under “classical” conditions.In the first part of this work, the design of chiral cations in HF/SbF5 media for their exploitation for stereocontrolled reactions was studied. The generated chiral ammonium-carboxonium superelectrophiles could be observed by low temperature in situ NMR experiments and analysed by X-ray diffraction of single-crystals. The reactivity of these species could be evaluated in the context of diastereoselective hydrofluorination reactions and Friedel-Crafts type cyclizations.In a second part, the superelectrophilic activation of alpha-aminonitriles allowed to develop a new reactivity of these compounds. The formation of ammonium-nitrilium dications was demonstrated by in situ NMR analysis at low temperature and crystallization in superacidic conditions HF/SbF5. This new methodology allowed the synthesis of novel chiral unsaturated piperidinones from amino acid derivatives.Finally, preliminary results of a new methodology of inert Csp3-H bonds functionalisation are presented in a third part. From unsaturated sulfonamides, nitrogen-containing heterocyclic compounds could be selectively synthesized under HF/SbF5 superacidic conditions without external activator.
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Thomas Cantin. Conception en milieu superacide de dications chiraux pour la synthèse de composés fluorés et/ou hétérocycliques azotés. Chimie de coordination. Université de Poitiers, 2019. Français. ⟨NNT : 2019POIT2290⟩. ⟨tel-02490867⟩

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