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Synthèse de nouvelles structures hélicoïdales incorporant des fonctions phosphorées. Applications en catalyse à l'or(I).

Abstract : Helicenes are ortho-fused polyaromatic compounds in which benzene rings are angularly annulated to give helically-shaped molecules.Molecular scaffolds with helical chirality have been rarely used for building phosphorus ligands and catalysts. In this context, with the purpose of accessing unprecedented chiral auxiliaries for organo- and organometallic catalysis, we have synthesized new series of phosphahelicenes. These compounds have been prepared via two differents procedures: a diastereoselective photochemical cyclization and a [2+2+2] cyclotrimerisation of alkynes, starting from phosphindole as a key building block. These phosphahelicenes have been evaluated as chiral ligand in gold promoted cyclisation reactions. These helical gold complexes proved to be highly efficient both in terms of catalytic activity and enantioselectivity in enyne cycloisomerizations, [2+2] and [4+2] cycloaddition reactions. Phosphahelicenes have also been used in phosphine organocatalysis. Good yields and enantiomercic excesses up to 97% have been obtained in [3+2] cyclizations between olefins and allenoates.
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  • HAL Id : tel-02426216, version 1

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Paul Aillard. Synthèse de nouvelles structures hélicoïdales incorporant des fonctions phosphorées. Applications en catalyse à l'or(I).. Chimie organique. Université Paris-Saclay, 2015. Français. ⟨NNT : 2015SACLS070⟩. ⟨tel-02426216⟩

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