Réactions de cycloisomérisation d'énynes dérivés de monoterpènes catalysées par du platine, du rhodium et de l'or ; synthèse de molécules à activité biologique potentielle / Ariadna Fuente-Hernandez  

Public ISBD Titre : Réactions de cycloisomérisation d'énynes dérivés de monoterpènes catalysées par du platine, du rhodium et de l'or ; synthèse de molécules à activité biologique potentielle Type de document : texte imprimé Auteurs : Ariadna Fuente-Hernandez ; Urrutigoïty, Martine, Directeur de thèse ; Jauregui-Haza, Ulises, Directeur de thèse Année de publication : 2010 Langues : Français (fre) Résumé : The transition metals catalyzed cycloisomerization reactions of enynes are a powerful tool in organic synthesis: they give access, in only one atom-economic step, to a variety of interesting mono- or bicyclic structures, comprising 1,4-diene, 1,3-diene, cyclobutene or cyclopropane moieties. In order to reach new molecules derived from monoterpenes, O-tethered 1,6- and 1,7- enynes were prepared starting from perillyl alcohol, nerol and isopulegol, and their reactivity in cycloisomerization reactions catalyzed by transition metals salts or complexes was studied. New bi- and tricyclic molecules containing cyclopropane, 1,3- or 1,4-dienes moieties were thus synthesized. All these molecules were purified and characterized by NMR techniques. Various catalytic systems described in the literature were compared: PtCl2, AuCl3, [AuCl(PPh3)/AgPF6] and Rh2Cl2(CO)4. We thus could show that the nature of the final product depended especially on the starting enyne structure but also on concerned catalyst. Moreover we highlighted that kinetics and selectivity could be modified under CO atmosphere. Analogously, an asymmetrical version of the reaction was explored in the case of the 1,6-enyne derived from perillyl alcohol by preparing platinum or gold complexes with chiral phosphorated ligands. The observed diastereoisomeric excess on two obtained cyclopropanes thus could be increased in the case of gold (I) complexes, but the values remain still modest. Finally, we undertook a preliminary study of the cycloisomerization reaction in ionic liquid with an aim of conceiving an effective system for catalyst recycling. Various ionic liquids and different extraction solvents were tested for 1,6-enyne derived from perillyl alcohol. The activity and the selectivity of various catalysts proved, resulted modified compared to the reaction in toluene and reproducibility problems appeared. This study will have to be continued in order to optimize the conditions of reaction and the catalysts recycling. Document : Thèse de doctorat Etablissement_delivrance : Université de Toulouse Date_soutenance : 16/04/2010 Ecole_doctorale : Sciences de la Matière (université Toulouse III P. Sabatier) Domaine : Chimie Organométallique et de Coordination Localisation : LCC En ligne : https://oatao.univ-toulouse.fr/7236/ Réactions de cycloisomérisation d'énynes dérivés de monoterpènes catalysées par du platine, du rhodium et de l'or ; synthèse de molécules à activité biologique potentielle [texte imprimé] / Ariadna Fuente-Hernandez ; Urrutigoïty, Martine, Directeur de thèse ; Jauregui-Haza, Ulises, Directeur de thèse . - 2010. Langues : Français (fre) Résumé : The transition metals catalyzed cycloisomerization reactions of enynes are a powerful tool in organic synthesis: they give access, in only one atom-economic step, to a variety of interesting mono- or bicyclic structures, comprising 1,4-diene, 1,3-diene, cyclobutene or cyclopropane moieties. In order to reach new molecules derived from monoterpenes, O-tethered 1,6- and 1,7- enynes were prepared starting from perillyl alcohol, nerol and isopulegol, and their reactivity in cycloisomerization reactions catalyzed by transition metals salts or complexes was studied. New bi- and tricyclic molecules containing cyclopropane, 1,3- or 1,4-dienes moieties were thus synthesized. All these molecules were purified and characterized by NMR techniques. Various catalytic systems described in the literature were compared: PtCl2, AuCl3, [AuCl(PPh3)/AgPF6] and Rh2Cl2(CO)4. We thus could show that the nature of the final product depended especially on the starting enyne structure but also on concerned catalyst. Moreover we highlighted that kinetics and selectivity could be modified under CO atmosphere. Analogously, an asymmetrical version of the reaction was explored in the case of the 1,6-enyne derived from perillyl alcohol by preparing platinum or gold complexes with chiral phosphorated ligands. The observed diastereoisomeric excess on two obtained cyclopropanes thus could be increased in the case of gold (I) complexes, but the values remain still modest. Finally, we undertook a preliminary study of the cycloisomerization reaction in ionic liquid with an aim of conceiving an effective system for catalyst recycling. Various ionic liquids and different extraction solvents were tested for 1,6-enyne derived from perillyl alcohol. The activity and the selectivity of various catalysts proved, resulted modified compared to the reaction in toluene and reproducibility problems appeared. This study will have to be continued in order to optimize the conditions of reaction and the catalysts recycling. Document : Thèse de doctorat Etablissement_delivrance : Université de Toulouse Date_soutenance : 16/04/2010 Ecole_doctorale : Sciences de la Matière (université Toulouse III P. Sabatier) Domaine : Chimie Organométallique et de Coordination Localisation : LCC En ligne : https://oatao.univ-toulouse.fr/7236/

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