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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Synthèse d'hétérocycles chiraux par catalyse à l'Au(I) et développement de nouveaux phosphahélicènes pour la catalyse énantiosélective / Au(I) catalyzed synthesis of chiral heterocycles and development of new phosphahelicenes as ligands for enantioselective catalysis.

Magné, Valentin 30 October 2017 (has links)
La catalyse à l’Au(I) est un outil très puissant pour la synthèse d’hétérocycles, en particulier dans des réactions impliquant des alcynes ou des allènes. Il est notamment possible de l'appliquer dans la synthèse de molécules complexes et dans un contexte de synthèse totale. Au cours de ce travail de thèse, nous avons développé de nouveaux complexes d'Au(I) chiraux, mais également de nouvelles réactions catalytiques. Nous avons développé une nouvelle famille de phosphines chirales énantiopures à chiralité hélicoïdale, obtenues par une étape-clé de cyclotrimérisation [2+2+2] d’alcynes. Elles ont pu être engagées dans des étapes de fonctionnalisations tardives, de manière à modifier l’environnement stérique et de modifier l’excès énantiomérique obtenu lors des étapes catalytiques. Nous avons étudié la complexation des phosphines avec des sels d'Au(I). Les phosphahélicènes obtenus ont ensuite été évalués dans une réaction de cycloisomérisation, et une bonne activité catalytique et un excès énantiomérique atteignant 94 % a été mesuré. De nouvelles réactions de synthèse de dérivés spiroindoliques par catalyse à l’Au(I) ont aussi été mises au point, par le biais de réactions de cyclisation désaromatisante sur des N-propargyl tryptamines. Ainsi, de nouveaux spirooxindoles et de nouvelles spiroindolénines ont été synthétisées. Enfin, une réaction énantiosélective de cycloisomérisation d'un allenyl pyrrole a été mise au point en utilisant des complexes d'Au(I) chiraux. Elle a conduit à un intermédiaire synthétique avancé, qui a été converti en quelques étapes en (-)-rhazinilame, un produit naturel d'intérêt biologique. Ainsi nous avons décrit la plus courte synthèse totale de ce composé. / Au(I) catalysis is a powerfull tool for heterocycles synthesis, particularly in reactions involving alkynes or allenes. It can be applied both in the synthesis of complex molecules or in the context of total synthesis. During this PhD work, we have developed new chiral Au(I) complexes and new catalytic reactions. We have developed a new family of enantiopure chiral phosphines featuring helicoïdal chirality, obtained by a [2+2+2] cyclotrimerization of alkynes as key step. They have been engaged in late stage functionalization, so as to modify the steric environment and to modify the enantiomeric excess obtained during the catalytic steps. We then studied the phosphine complexation with Au(I) salts. The corresponding phosphahelicenes have been engaged in cycloisomerization reactions. With the best catalyst, a good catalytic activity and an enantiomeric excess of 94 % have been measured. New reactions catalyzed by Au(I) complexes for the synthesis of spiroindolic compounds have been studied, by dearomatizing cyclisation of N-propargyl tryptamines. With this approach, new spirooxindoles and new spiroindolenines have been synthetized. Finally, the enantioselective cycloisomerization of an allenyl pyrrole was studied with chiral Au(I) catalysts. This reaction led to an advanced intermediate, which was converted in few steps to (-)-rhazinilam, a natural product featuring interesting bioactivities. Thus we have described the shortest total synthesis of this natural compound.
2

Catalyseurs d'oxydation et carbènes hétérocycliques organophosphorés

El Kazzi, A. 05 December 2008 (has links) (PDF)
Dans la première partie, est présentée la synthèse d'une nouvelle famille de catalyseurs d'oxydation phosphorés performants et sélectifs. Ainsi nous avons mis au point la synthèse des imines N-phosphonio qui permettent de réaliser l'époxydation catalytique des oléfines. Une étude détaillée montre comment on peut facilement moduler la réactivité de la fonction imine en jouant sur la nature des substituants, et ainsi pouvoir adapter le catalyseur au type de substrat à oxyder. Dans la deuxième partie, est décrite une nouvelle voie de synthèse, simple et courte, pour les précurseurs des carbènes vinylidènephosphoranes. Cette voie de synthèse autorise une grande variation dans le choix des substituants ce qui devrait permettre de moduler facilement les propriétés de cette nouvelle famille de carbènes. Les premiers résultats montrent que ces carbènes présentent un caractère ambiphile prononcé avec une nucléophilie exacerbée, comme prévu par des calculs théoriques. Les premiers résultats en chimie de coordination sont également présentés et le premier complexe de Au(I) a été isolé et caractérisé par diffraction des rayons X.
3

Chemical tools for antimalarial drug development : synthesis of plasmodione analogues and 13C-enriched plasmodione for drug metabolomics investigations / Outils moléculaires pour le développement de médicaments antipaludiques : synthèse d’analogues de plasmodione et de 13C18-plasmodione pour des recherches en métabolomique

Feng, Liwen 11 July 2017 (has links)
Le paludisme est une maladie parasitaire tropicale menaçant les populations dans les zones tropicales et sub-tropicales, en particulier les jeunes enfants en Afrique. En raison des résistances aux médicaments antipaludiques qui se sont propagées dans le monde entier au cours des 50 dernières années, de nouveaux médicaments sont vraiment nécessaires. La plasmodione (série benzylmenadione) a été identifiée comme un médicament-candidat antipaludique puissant, agissant selon une bioactivation rédox sur les stades sanguins asexués et sexués jeunes, mais son métabolisme est inconnu. Par conséquent, afin d'identifier les structures des métabolites actifs générés par la plasmodione antipaludique, la synthèse complète de la plasmodione 13C18-enrichie a été conçue et réalisée en 10 étapes. En outre, le procédé d'extraction pour l'étude du métabolisme de la molécule a été établi à partir de globules rouges parasités traités par la plasmodione 13C18-enrichie. D'autre part, la préparation de dérivés oxétane et N-alkylaryl de plasmodione avec une solubilité potentielle améliorée a également été réalisée par substitution nucléophilie aromatique (SNAr) et réaction de couplage Buchwald-Hartwig catalysée par le palladium, respectivement. Enfin, un complexe d'or (I) phosphole, connu comme un inhibiteur irréversible et puissant de la thiorédoxine réductase séléno-dépendante humaine, a été synthétisé et son profil antiparasitaire a été étudié sur de nombreux parasites pathogènes pour l’homme, protozoaires et helminthes en cultures. / Malaria is a tropical parasitic disease threatening populations in tropical and sub-tropical areas, especially young children in Africa. Due to the drug resistance spread all over the world in the past 50 years, new drugs are urgently needed. Plasmodione (benzylmenadione series) had been identified as a potent anti-malarial early lead drug, acting through a redox bioactivation on asexual and young sexual blood stages, but its drug metabolism is unknown. Therefore, in order to identify the structures of the active drug metabolites generated from the antimalarial plasmodione, fully 13C18-enriched-plasmodione synthesis was designed and performed in 10 steps. Furthermore, the extraction method for the drug metabolism study was established from 13C18-enriched plasmodione-treated parasitized red blood cells. On the other hand, the preparation of oxetane and N-alkylaryl derivatives of plasmodione with potential improved solubility was also investigated through aromatic nucleophilic substitution (SNAr) and palladium-catalyzed Buchwald-Hartwig coupling reaction, respectively. Finally, a gold(I) phosphole complex, known as an irreversible and potent inhibitor of the human seleno-dependent thioredoxin reductase, was synthetized and its antiparasitic profile investigated against a panel of parasites, protozoans and helminthes in cultures.
4

Development of an Optical Carbon Dioxide Sensor and Modeling of Metal-Metal Interactions for Sensor Applications

Ericson, Megan 12 1900 (has links)
An investigation of luminescent sensing has been presented. Neutral Red, a common pH luminescent sensor, was shown to be an effective carbon dioxide sensor for the first time. Sensing experiments were performed both through fluorometric and fluorescent microscopy studies, giving rise to the possibility of carbon dioxide sensing for biological applications. Neutral Red was benchmarked against the well-established carbon dioxide sensor Pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt), HPTS. Neutral Red was shown to have improved response times and higher consistency within the sensing drift compared to HPTS. Trinuclear Au(I) complexes have previously shown to sense metal ions through changes in their luminescent properties. A computational study on d10-d10 interactions, which exist in complexes where Cu+, Ag+, and Au+ are intercalated with [Au(μ-C2,N3-ethylImidazolate)]3 in the form of both half and full sandwich adducts. Binding energies, total density plots, and Morse and Dunham analyses of potential energy surfaces are employed to better understand the metal-metal interactions and the effects of electron correlation, basis set superposition error, and dispersion of metallophilic interactions of the adduct complexes. As metal-metal interactions within these types of complexes become better understood, the tuning of trinuclear Au(I) complexes for luminescent sensing of metals becomes increasingly possible.
5

Síntese e caracterização de complexos de Cu(I), Cu(II) E Au(I) com ligantes triazenidos contendo substituintes triazóis / Synthesis and characterization of Cu(I), Cu(II) AND Au(I) complexes with triazenido ligands containing triazole substituents

Morgan, Dieisson 29 November 2013 (has links)
Triazenido ions are isoelectronic to amidinato anions,[R'N C(R)=NR']- and have a broad versatility in coordination chemistry. Metal complexes including triazenido ligands find applications in various areas of chemistry. Triazenes and complexes including triazole derivatives show extensive applicability as for example in supramolecular chemistry and pharmacological compounds. This work presents deals with the study of new triazene derivatives with triazole substituents resulting from the click reactions, acting as ligands in complexes with Cu(I), Cu(II) and Au(I). The following ligands 1,3-bis(2-azidophenyl)triazene (2), 1-(methyl)-3-(2-(4-phenyl-1,2,3-triazole)triazene-N-oxide (4), 1-(phenyl)-3-(2-(4-phenyl-1,2,3-triazole)triazene (5), 1,3-bis(2-(4-phenyl-1,2,3-triazole)triazene (6) and, complexes 1,3-bis(2-azidophenyl)triazenide-κN11- triphenylphosphine-gold(I) (2a), bis-{1-(methyl)-3-[2-(4-phenyl-1,2,3-triazole-κN2)]triazenide-1-oxide-κ2N3,O}copper(II) (4b), 1-(phenyl)-3-(2-(4-phenyl-1,2,3-triazole)triazenide-κN- triphenylphosphine-κP-gold(I) (5a), 1,3-bis(2-(4-phenyl-1,2,3-triazole)triazenide-κN- triphenylphosphine-κP-gold(I) (6a), bis[1,3-bis(2-(4-phenyl-1,2,3-triazole-κN2)-μ-N3-triazenide]-κN11,κN13 copper(I)κN13,κN11´copper(I) (Cu Cu) (6b) were investigated. The compounds were characterized by IR, UV-Vis and NMR (1H e 13C) spectroscopy, low or high resolution mass spectrometry (EI, ESI, ESI(+)-TOF and ESI(-)-TOF) and X-ray diffraction on single crystal. Triazene (2) and complex (2a) exhibit intramolecular assembling through classical and non-classical hydrogen bonding. Complexes with Au(I), (2a), (5a) e (6a), the metal atom show linear coordination geometry. The metal atom in complex (6b) shows a T distorted coordination geometry, which is extended to a quadratic coordination resulting from d10 d10 interactions between Cu(I) ions. Triazene (6) and its respective complexes (6a) e (6b) exhibit intermolecular interactions of the type C−H···M. Antibacterial activity of triazene (5) and complex (5a) were assayed resulting to be inactive against the bacteria tested. / Os compostos triazenidos são isoeletrônicos a íons amidinatos [R'NH C(R)=NR'], e têm sido usados com sucesso na química de coordenação. A complexação a íons metálicos possibilita a sua aplicação em diversas áreas da química. Assim como os triazenos, os triazóis possuem vasta aplicabilidade, desde a química supramolecular até a área farmacológica. Este trabalho apresenta o estudo inédito de pré-ligantes triazenos contendo substituintes triazóis os quais foram obtidos a partir de reações de Click, e seus respectivos complexos de Cu(I), Cu(II) e Au(I). Foram sintetizados os pré-ligantes 1,3-bis(2-azidofenil)triazeno (2), 1-(metil)-3-(2-(4-fenil-1,2,3-triazol)triazeno-N-óxido (4), 1-(fenil)-3-(2-(4-fenil-1,2,3-triazol)triazeno (5), 1,3-bis(2-(4-fenil-1,2,3-triazol)triazeno (6) e os complexos 1,3-bis(2-azidofenil)triazenido-κN11-trifenilfosfina-ouro(I) (2a), bis-{1-(metil)-3-[2-(4-fenil-1,2,3-triazol-κN2)]triazenido-1-óxido-κ2N3,O}cobre(II) (4b), 1-(fenil)-3-(2-(4-fenil-1,2,3-triazol)triazenido-κN-trifenilfosfina-κP-ouro(I) (5a), 1,3-bis(2-(4-fenil-1,2,3-triazol)triazenido-κN-trifenilfosfina-κP-ouro(I) (6a), bis[1,3-bis(2-(4-fenil-1,2,3-triazol-κN2)-μ-N3-triazenido]-κN11,κN13 - cobre(I)κN13,κN11´cobre(I) (Cu Cu) (6b). Estes foram caracterizados por espectroscopia de IV, UV-Vis e RMN (1H e 13C), espectrometria de massas de baixa ou alta resolução (EI, ESI, ESI(+)-TOF e ESI(-)-TOF) e difração de raios X em monocristal. O triazeno (2) e complexo (2a) apresentam ligações de hidrogênio intermoleculares e intramoleculares do tipo clássica e não-clássica. Os complexos de Au(I), (2a), (5a) e (6a) possuem geometria de coordenação linear. O complexo (6b) apresenta uma geometria T distorcida, a qual é estendida para quadrática pela interação d10 d10 entre os átomos de Cu(I), o triazeno (6) e seus complexos (6a) e (6b) apresentam ainda ligações intermoleculares do tipo C−H···M. Foi testada a atividade antibacteriana do triazeno (5) e o complexo (5a), os quais mostraram-se inativos frente às bactérias testadas.
6

Síntese, análise cristalográfica e atividade biológica de complexos com ligantes triazenidos com fragmentos orto-halofenila e para-sulfonamidafenila / Synthesis, crystallographic analysis and biological activity of the complexes with triazenides ligands with orto-halophenyl and para-sulfonamidephenyl fragments

Zambiazi, Priscilla Jussiane 08 March 2013 (has links)
Conselho Nacional de Desenvolvimento Científico e Tecnológico / This study shows the triazenes ligands and complexes Pd(II), K+ and Au(I) obtained from reactions of the ligands with fragments para-sulfonamidephenyl, comprising triazene ligand 1,3-bis (4 - sulfonamidephenyl) (1) and the complex {trans-Bis[1,3-bis(4-sulfonamidephenyl)triazenide-κN1]bis(pyridine-κN)palladium(II)}{tetra(pyridine-κN)palladium(II)}bis(potssium)·water (2) and for compounds containing orto-halophenyl fragments represented by [1,3-bis(2-fluorophenyl)triazenide-κN1](triphenylphosphine- κP)gold(I) (3), [1,3-bis(2-chlorinephenyl)triazenide-κN1](triphenylphosphine-κP)gold(I) (4), [1,3-bis(2-bromidephenyl)triazenide-κN1](triphenylphosphine-κP)gold(I) (5) and [1,3-bis(2-iodinephenyl)triazenide-κN1](triphenylphosphine - κP)gold(I) (6) complexes. The compounds reported were characterized by X-ray diffraction on single crystal, and their structures in solid state are formed through supramolecular arrangements via classical and non-classical hydrogen bonding, as in the case of the compounds with the sulfonamide grouping, one can observe the formation of supramolecular synthons. In complexes 4, 5 and 6 it is observed to occur interactions halogen···halogen characterized by the formation of dimeric units associated by a center of inversion, besides having geometries classified by the angle of the links formed between the halogen and carbon atoms. Compounds 1, 2, 3, 4, 5 and 6 were subjected to evaluation front of biological activity, such as plasmidial DNA cleavage studies, evaluation of cytotoxicity and antibacterial activity, showing promising results. / Este trabalho apresenta o estudo de ligantes triazenos e complexos de Pd(II), K+ e Au(I) obtidos a partir de reações com os ligantes com fragmentos para-sulfonamidafenila compreendendo o ligante 1,3-bis-(4-sulfonamidafenil)triazeno (1) e o complexo {trans-Bis[1,3-bis(4-sulfonamidafenil)triazenido-κN1]bis(piridina-κN)paládio(II)}{tetra(piridina-κN)paládio(II)}bis(potássio)·água (2) e para compostos contendo fragmentos orto-halofenila representados pelos complexos [1,3-bis(2-fluorofenil)triazenido-κN1](trifenilfosfina- κP)ouro(I) (3), [1,3-bis(2-clorofenil)triazenido-κN1](trifenilfosfina- κP)ouro(I) (4), [1,3-bis(2-bromofenil)triazenido-κN1](trifenilfosfina- κP)ouro(I) (5) e [1,3-bis(2-iodofenil)triazenido-κ-N1](trifenilfosfina- κP)ouro(I) (6). Os compostos relatados foram caracterizados por difração de raios X em monocristal, e suas estruturas no estado sólido são formadas através de arranjos supramoleculares via ligações de hidrogênio clássicas e não clássicas, como no caso dos compostos com o grupamento sulfonamida, pode-se observar a formação de synthons supramoleculares. Nos complexos 4, 5 e 6 é observada a ocorrência de interações halogênio···halogênio caracterizadas pela formação de unidades díméricas associadas por um centro de inversão, além de apresentarem geometrias classificadas pelo ângulo de ligações formado entre os átomos de halogênio e carbono. Os compostos 1, 2, 3, 4, 5 e 6 foram submetidos a avaliação frente a atividade biológica, como estudos na clivagem do DNA plasmidial, avaliação da citotoxicidade e atividade antibacteriana, mostrando resultados promissores.

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