10 research outputs found
C-C and C-heteroatom bonds formation by copper catalyst or via ruthenium complexes
Cette thĂšse se situe dans le cadre gĂ©nĂ©ral de la recherche de nouvelles mĂ©thodes de synthĂšse peu couteuses et Ă©co-compatibles permettant de valoriser certaines molĂ©cules en accĂ©dant Ă des composĂ©s intĂ©ressants dans plusieurs domaines comme la chimie des matĂ©riaux, pharmaceutique et organique. Lâobjectif consiste Ă crĂ©er des nouvelles liaisons C-C et C-hĂ©tĂ©roatome sous un contrĂŽle de sĂ©lectivitĂ© par catalyse avec des mĂ©taux de transition.Dans une premiĂšre partie, une difonctionnalisation des alcĂšnes a Ă©tĂ© rĂ©alisĂ©e par catalyse au cuivre pour aboutir Ă lâoxazolidinone qui comporte un squelette important prĂ©sent dans de nombreuses molĂ©cules de haute activitĂ© biologique.Dans la deuxiĂšme partie, des ligands pyridil dicĂ©tones associĂ©s Ă un catalyseur de cuivre ont Ă©tĂ© employĂ© dans lâarylation de lâammoniac aqueux. Ce systĂšme sâapplique au couplage Ă partir des aryles iodĂ©s et bromĂ©s dans des conditions douces pour donner lâaniline, un intĂ©ressant prĂ©curseur de molĂ©cules dâintĂ©rĂȘt surtout pour la chimie de matĂ©riaux.Dans la troisiĂšme partie, des rĂ©actions dâhydrofonctionnalisation des allĂšnes catalysĂ©es au cuivre ont Ă©tĂ© dĂ©veloppĂ©es pour crĂ©er de nouvelles liaisons C-C, C-O et C-P. Ces rĂ©actions permettent dâaccĂ©der sĂ©lectivement Ă des produits allyliques qui pourront ĂȘtre des intermĂ©diaires intĂ©ressants dans la chimie organique.La derniĂšre partie consiste Ă mettre en Ćuvre un nouveau complexe de ruthĂ©nium visant Ă rĂ©aliser une amination directe du phĂ©nol sans aucune prĂ©-activation.This thesis is a part of general research for novel, cheap and eco-friendly methods for the valorization of some subtrates and for the synthesis of interesting molecules in various fields such as material, pharmaceutical and organic chemistry. The main goal is to create new C-C and C-heteroatom bonds with high selectivity by using transition metal-catalysts.In the first part, a copper-catalyzed alkenes difunctionnalization has been realized to afford oxazolidinone, which contains an interesting moiety present in various bioactive molecules.In the second part, novel pyridyl diketone ligands associated to a copper catalyst have been employed in ammonia arylation reaction. This system led the amination of aryl iodides and bromides in mild temperature conditions to afford aniline derivatives, valuable molecules for the material chemistry.In the third part, we developed copper-catalyzed hydrofunctionnalizations of allenes to create new C-C, C-O and C-P bonds. These methods afford selectively the allylic products, that could be valuable key intermediates in organic chemistry.The last part consists in the developement of a novel ruthenium complex to allow the direct phenol amination without any previous activation.Key-words : alkenes, aniline, copper, allenes, hydrofunctionnalization, phenol, rutheniu
Formation de liaisons C-C et C-hétéroatome par catalyse au cuivre ou en présence de complexes de ruthénium
This thesis is a part of general research for novel, cheap and eco-friendly methods for the valorization of some subtrates and for the synthesis of interesting molecules in various fields such as material, pharmaceutical and organic chemistry. The main goal is to create new C-C and C-heteroatom bonds with high selectivity by using transition metal-catalysts.In the first part, a copper-catalyzed alkenes difunctionnalization has been realized to afford oxazolidinone, which contains an interesting moiety present in various bioactive molecules.In the second part, novel pyridyl diketone ligands associated to a copper catalyst have been employed in ammonia arylation reaction. This system led the amination of aryl iodides and bromides in mild temperature conditions to afford aniline derivatives, valuable molecules for the material chemistry.In the third part, we developed copper-catalyzed hydrofunctionnalizations of allenes to create new C-C, C-O and C-P bonds. These methods afford selectively the allylic products, that could be valuable key intermediates in organic chemistry.The last part consists in the developement of a novel ruthenium complex to allow the direct phenol amination without any previous activation.Key-words : alkenes, aniline, copper, allenes, hydrofunctionnalization, phenol, rutheniumCette thĂšse se situe dans le cadre gĂ©nĂ©ral de la recherche de nouvelles mĂ©thodes de synthĂšse peu couteuses et Ă©co-compatibles permettant de valoriser certaines molĂ©cules en accĂ©dant Ă des composĂ©s intĂ©ressants dans plusieurs domaines comme la chimie des matĂ©riaux, pharmaceutique et organique. Lâobjectif consiste Ă crĂ©er des nouvelles liaisons C-C et C-hĂ©tĂ©roatome sous un contrĂŽle de sĂ©lectivitĂ© par catalyse avec des mĂ©taux de transition.Dans une premiĂšre partie, une difonctionnalisation des alcĂšnes a Ă©tĂ© rĂ©alisĂ©e par catalyse au cuivre pour aboutir Ă lâoxazolidinone qui comporte un squelette important prĂ©sent dans de nombreuses molĂ©cules de haute activitĂ© biologique.Dans la deuxiĂšme partie, des ligands pyridil dicĂ©tones associĂ©s Ă un catalyseur de cuivre ont Ă©tĂ© employĂ© dans lâarylation de lâammoniac aqueux. Ce systĂšme sâapplique au couplage Ă partir des aryles iodĂ©s et bromĂ©s dans des conditions douces pour donner lâaniline, un intĂ©ressant prĂ©curseur de molĂ©cules dâintĂ©rĂȘt surtout pour la chimie de matĂ©riaux.Dans la troisiĂšme partie, des rĂ©actions dâhydrofonctionnalisation des allĂšnes catalysĂ©es au cuivre ont Ă©tĂ© dĂ©veloppĂ©es pour crĂ©er de nouvelles liaisons C-C, C-O et C-P. Ces rĂ©actions permettent dâaccĂ©der sĂ©lectivement Ă des produits allyliques qui pourront ĂȘtre des intermĂ©diaires intĂ©ressants dans la chimie organique.La derniĂšre partie consiste Ă mettre en Ćuvre un nouveau complexe de ruthĂ©nium visant Ă rĂ©aliser une amination directe du phĂ©nol sans aucune prĂ©-activation
Formation de liaisons C-C et C-hétéroatome par catalyse au cuivre ou en présence de complexes de ruthénium
This thesis is a part of general research for novel, cheap and eco-friendly methods for the valorization of some subtrates and for the synthesis of interesting molecules in various fields such as material, pharmaceutical and organic chemistry. The main goal is to create new C-C and C-heteroatom bonds with high selectivity by using transition metal-catalysts.In the first part, a copper-catalyzed alkenes difunctionnalization has been realized to afford oxazolidinone, which contains an interesting moiety present in various bioactive molecules.In the second part, novel pyridyl diketone ligands associated to a copper catalyst have been employed in ammonia arylation reaction. This system led the amination of aryl iodides and bromides in mild temperature conditions to afford aniline derivatives, valuable molecules for the material chemistry.In the third part, we developed copper-catalyzed hydrofunctionnalizations of allenes to create new C-C, C-O and C-P bonds. These methods afford selectively the allylic products, that could be valuable key intermediates in organic chemistry.The last part consists in the developement of a novel ruthenium complex to allow the direct phenol amination without any previous activation.Key-words : alkenes, aniline, copper, allenes, hydrofunctionnalization, phenol, rutheniumCette thĂšse se situe dans le cadre gĂ©nĂ©ral de la recherche de nouvelles mĂ©thodes de synthĂšse peu couteuses et Ă©co-compatibles permettant de valoriser certaines molĂ©cules en accĂ©dant Ă des composĂ©s intĂ©ressants dans plusieurs domaines comme la chimie des matĂ©riaux, pharmaceutique et organique. Lâobjectif consiste Ă crĂ©er des nouvelles liaisons C-C et C-hĂ©tĂ©roatome sous un contrĂŽle de sĂ©lectivitĂ© par catalyse avec des mĂ©taux de transition.Dans une premiĂšre partie, une difonctionnalisation des alcĂšnes a Ă©tĂ© rĂ©alisĂ©e par catalyse au cuivre pour aboutir Ă lâoxazolidinone qui comporte un squelette important prĂ©sent dans de nombreuses molĂ©cules de haute activitĂ© biologique.Dans la deuxiĂšme partie, des ligands pyridil dicĂ©tones associĂ©s Ă un catalyseur de cuivre ont Ă©tĂ© employĂ© dans lâarylation de lâammoniac aqueux. Ce systĂšme sâapplique au couplage Ă partir des aryles iodĂ©s et bromĂ©s dans des conditions douces pour donner lâaniline, un intĂ©ressant prĂ©curseur de molĂ©cules dâintĂ©rĂȘt surtout pour la chimie de matĂ©riaux.Dans la troisiĂšme partie, des rĂ©actions dâhydrofonctionnalisation des allĂšnes catalysĂ©es au cuivre ont Ă©tĂ© dĂ©veloppĂ©es pour crĂ©er de nouvelles liaisons C-C, C-O et C-P. Ces rĂ©actions permettent dâaccĂ©der sĂ©lectivement Ă des produits allyliques qui pourront ĂȘtre des intermĂ©diaires intĂ©ressants dans la chimie organique.La derniĂšre partie consiste Ă mettre en Ćuvre un nouveau complexe de ruthĂ©nium visant Ă rĂ©aliser une amination directe du phĂ©nol sans aucune prĂ©-activation
Transition MetalâCatalyzed Intermolecular Hydroarylation of Allenes
International audienc
Regio- and Stereoselective Copper-Catalyzed Allylation of 1,3-Dicarbonyl Compounds with Terminal Allenes
International audienceSimple ligand-free copper systems were found as efficient catalysts for the addition of 1,3-dicarbonyl compounds to N-allenyl derivatives. This highly regio- and stereoselective reaction has been accomplished in the presence of malonates, 1,3-ketoesters, and 1,3-diketones with good to excellent yields under mild conditions. This methodology represents the first allylation of 1,3-dicarbonyl compounds with allenes catalyzed by copper
Regio- and Stereoselective Copper-Catalyzed Allylation of 1,3-Dicarbonyl Compounds with Terminal Allenes
Simple ligand-free copper systems
were found as efficient catalysts
for the addition of 1,3-dicarbonyl compounds to <i>N</i>-allenyl derivatives. This highly regio- and stereoselective reaction
has been accomplished in the presence of malonates, 1,3-ketoesters,
and 1,3-diketones with good to excellent yields under mild conditions.
This methodology represents the first allylation of 1,3-dicarbonyl
compounds with allenes catalyzed by copper
Regio- and Stereoselective Copper-Catalyzed Allylation of 1,3-Dicarbonyl Compounds with Terminal Allenes
Simple ligand-free copper systems
were found as efficient catalysts
for the addition of 1,3-dicarbonyl compounds to <i>N</i>-allenyl derivatives. This highly regio- and stereoselective reaction
has been accomplished in the presence of malonates, 1,3-ketoesters,
and 1,3-diketones with good to excellent yields under mild conditions.
This methodology represents the first allylation of 1,3-dicarbonyl
compounds with allenes catalyzed by copper
Mild temperature amination of aryl iodides and aryl bromides with aqueous ammonia in the presence of CuBr and pyridyldiketone ligands
Highlightsâą Copper-catalyzed arylation of aqueous ammonia from aromatic halides.âą Synthesis of aniline derivatives.âą Mild temperature conditions in the presence of ambidentate pyridyldiketone ligands.International audienceCatalytic systems based on copper and simple ligands of ambidentate pyridyldiketone type were used in direct amination of aryl iodides and bromides with aqueous ammonia in one of the mildest conditions described in the literature, with reaction temperature ranging between 25 and 80âŻÂ°C
Mild Temperature Copper-Catalyzed Amination of Aryl Halides with Aqueous Ammonia in the Presence of Pyridyldiketone Ligands
Ambidentate ligand pyridyldiketones were used in combination with copper to catalyze amination of aryl halides under very mild temperatures with aqueous ammonia. This novel catalytic system allow efficient coupling in one of the smoothest conditions ever reported in literature