Skip to Main content Skip to Navigation
Theses

Nouvelles applications des proazaphosphatranes et molécules apparentées : vers la catalyse en espace confiné et en milieu hétérogène

Abstract : The work described in this PhD thesis deals with the chemistry of proazaphosphatrane-type superbases, which are highly reactive bicyclic phosphorous systems largely applied in catalysis. The main goal of these investigations was to devise new applications for their use in catalysis. In this way, several strategies were followed, with an emphasis on their molecular confinement and use in interfacial catalytic systems. In the first part, the manuscript describes the synthesis and characterisation of a supramolecular proazaphosphatrane obtained via the enclosing of a proazaphosphatrane moiety in a hemicryptophane-type macrobicyclic cavity. In parallel, the semi-preparative scale resolution of two macrobicyclic intermediates allowed us to assign their absolute configurations. In the second part, the synthesis and characterisation of a new class of superbases supported on mesoporous silica was achieved. The synthesis was followed by their application in base-catalysed organic reactions. The last part reports the use of their conjugate acids, or azaphosphatranes, in phase transfer catalysis. Their usefulness as achiral phase transfer agents in four relevant reactions was thus determined. The thesis ends with an introduction into asymmetric phase transfer catalysis, using enantiopure azaphosphatranes.
Document type :
Theses
Complete list of metadatas

Cited literature [91 references]  Display  Hide  Download

https://tel.archives-ouvertes.fr/tel-00660221
Contributor : Abes Star :  Contact
Submitted on : Monday, January 16, 2012 - 11:22:35 AM
Last modification on : Wednesday, November 20, 2019 - 2:43:16 AM
Long-term archiving on: : Tuesday, April 17, 2012 - 2:25:37 AM

File

Dimitrov_Raytchev_Pascal_2011_...
Version validated by the jury (STAR)

Identifiers

  • HAL Id : tel-00660221, version 1

Citation

Pascal Dimitrov Raytchev. Nouvelles applications des proazaphosphatranes et molécules apparentées : vers la catalyse en espace confiné et en milieu hétérogène. Autre. Ecole normale supérieure de lyon - ENS LYON, 2011. Français. ⟨NNT : 2011ENSL0648⟩. ⟨tel-00660221⟩

Share

Metrics

Record views

721

Files downloads

2954