Carbonylation reaction of natural substrates extracted from plants / El Karroumi, Jamal  

Public ISBD Titre : Carbonylation reaction of natural substrates extracted from plants Type de document : texte imprimé Auteurs : El Karroumi, Jamal ; Urrutigoïty, Martine, Directeur de thèse Année de publication : 2014 Langues : Anglais (eng) Tags : CARBONYLATION  TERPENES  PALLADIUM  ATLAS CEDAR  ALLYLIC ALCOHOL Résumé : "The catalytic functionnalisation of the natural substrates have been developped to increase their own biological activity or to give them new biological properties. The reactions such as hydroformylation, alkoxycarbonylation and cyclocarbonylation in presence of carbon monoxide catalyzed by rhodium or palladium complexes or cycloisomerisation catalyzed by gold or platinium complexes give an access to new interesting molecules with high selectivity. In first part we have been interested in study of the essential oil of the Atlas Cedar (Cedrus Atlantica). We focused in this study on the oxygenated fraction, which contains the two sesquiterpenic ketone,isomers Z- and E-?-atlantone. Starting from allylic alcohols derived from ?-atlantone, the cyclocarbonylation reaction catalyzed by palladium complexes have been investigated. This reaction provide a mixture of five and six membered ring lactones with excellent conversion and excellent chemioselectivity. Different catalytic systems [PdCl2L2]/SnCl2.2H2O or [Pd(OAc)2]/L have been studied. The regiochemical control depends on the nature of the ligand L. The monophosphine ligands favor the formation of the six-membered ring lactones obtained as two diastereomers, while the diphosphine ligands allow the formation of the five- membered ring lactone obtained as four diastereomers. These new lactones were fully characterized by 1D and 2D NMR and mass spectrometry. Monocrystals of the six- and five-membered ring lactones suitable for X-ray diffraction analysis have been obtained. In a second part the hydroformylation reaction of estragol, a natural allylbenzene extracted from the essential oil of estragon, have been studied with the catalytic system [Rh(cod)(OMe)]2/phospholes. All the phosphole ligands show good activities and chemoselectivities in the hydroformylation of estragol and affords the linear aldehyde corresponding as a major product. In a preliminary study, we have investigated the cycloisomerisation reaction of o-tethered enynes derived from ?-atlantones catalyzed by gold or platinum complexes." Document : Thèse de Doctorat Etablissement_delivrance : Institut National Polytechnique de Toulouse - INPT etUniversité Cadi Ayyad (Marrakech, Maroc) Date_soutenance : 04/07/2014 Ecole_doctorale : Sciences de la Matière (Toulouse) Domaine : Chimie/Chimie de coordination En ligne : http://ethesis.inp-toulouse.fr/archive/00002701/ Carbonylation reaction of natural substrates extracted from plants [texte imprimé] / El Karroumi, Jamal ; Urrutigoïty, Martine, Directeur de thèse . - 2014. Langues : Anglais (eng) Tags : CARBONYLATION  TERPENES  PALLADIUM  ATLAS CEDAR  ALLYLIC ALCOHOL Résumé : "The catalytic functionnalisation of the natural substrates have been developped to increase their own biological activity or to give them new biological properties. The reactions such as hydroformylation, alkoxycarbonylation and cyclocarbonylation in presence of carbon monoxide catalyzed by rhodium or palladium complexes or cycloisomerisation catalyzed by gold or platinium complexes give an access to new interesting molecules with high selectivity. In first part we have been interested in study of the essential oil of the Atlas Cedar (Cedrus Atlantica). We focused in this study on the oxygenated fraction, which contains the two sesquiterpenic ketone,isomers Z- and E-?-atlantone. Starting from allylic alcohols derived from ?-atlantone, the cyclocarbonylation reaction catalyzed by palladium complexes have been investigated. This reaction provide a mixture of five and six membered ring lactones with excellent conversion and excellent chemioselectivity. Different catalytic systems [PdCl2L2]/SnCl2.2H2O or [Pd(OAc)2]/L have been studied. The regiochemical control depends on the nature of the ligand L. The monophosphine ligands favor the formation of the six-membered ring lactones obtained as two diastereomers, while the diphosphine ligands allow the formation of the five- membered ring lactone obtained as four diastereomers. These new lactones were fully characterized by 1D and 2D NMR and mass spectrometry. Monocrystals of the six- and five-membered ring lactones suitable for X-ray diffraction analysis have been obtained. In a second part the hydroformylation reaction of estragol, a natural allylbenzene extracted from the essential oil of estragon, have been studied with the catalytic system [Rh(cod)(OMe)]2/phospholes. All the phosphole ligands show good activities and chemoselectivities in the hydroformylation of estragol and affords the linear aldehyde corresponding as a major product. In a preliminary study, we have investigated the cycloisomerisation reaction of o-tethered enynes derived from ?-atlantones catalyzed by gold or platinum complexes." Document : Thèse de Doctorat Etablissement_delivrance : Institut National Polytechnique de Toulouse - INPT etUniversité Cadi Ayyad (Marrakech, Maroc) Date_soutenance : 04/07/2014 Ecole_doctorale : Sciences de la Matière (Toulouse) Domaine : Chimie/Chimie de coordination En ligne : http://ethesis.inp-toulouse.fr/archive/00002701/

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