Aspects non usuels de la chimie des azaphosphatranes et proazaphosphatranes : application en organocatalyse

Abstract : Proazaphosphatranes are highly reactive phosphorous bicyclic compounds also called Verkade’s superbases and the azaphosphatranes are their acidic counterparts. The goal of the work is to investigate the modifications of the properties of these compounds when they are in confined space. Firstly, the superbases were encapsulated into hemicryptophane host compounds (molecular containers created from the association of a cyclotriveratrylene unit with another C3-symmetric moiety). Modifications in the basicity of the supramolecular superbases depending on the substitution pattern around the phosphorous were evidenced compare to the molecules lacking the cavity. The catalytic activity of a superbase was investigated on a nucleophilic and a basic reaction. The azaphosphatranes were then used to catalyze the cycloaddition of carbon dioxide (CO2) to epoxides to form a cyclic carbonate. Enhancements of the stability of encaged catalyst were demonstrated. Finally, an azaphophatrane was immobilized on mesoporous silica leading to a heterogeneous catalyst.
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Bastien Chatelet. Aspects non usuels de la chimie des azaphosphatranes et proazaphosphatranes : application en organocatalyse. Autre. Ecole normale supérieure de lyon - ENS LYON, 2013. Français. ⟨NNT : 2013ENSL0839⟩. ⟨tel-01070639⟩

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