Dissertations / Theses on the topic 'Synthèse de polyènes'
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Ramondenc, Yvan. "Nouveaux réactifs de polyvinylogation. Synthèse de tri-, tétra, et hexa-ènals. Accès à des polyènes linéaires." Rouen, 1992. http://www.theses.fr/1992ROUE5002.
Brun, Elodie. "Synthèse stéréosélective de 1,3-polyols - synthèse du (+)-cryptocaryol A et du squelette carboné de la filipine III." Thesis, Paris 6, 2015. http://www.theses.fr/2015PA066433/document.
1,3-Polyols are present in a large variety of biologically active natural products. However, right now only a few general and efficient methods have been described to access these compounds in a stereocontrolled manner. We were particularly interested in the synthesis of 1,3,5,7-tetraols and a method has been developed to prepare these compounds, using two successive Prins cyclizations followed by a reductive cleavage of the resulting bis-tetrahydropyran. This efficient method allows the access to all the diastereomers of these tetraols and has successfully been applied to the synthesis of (+)-cryptocaryol A, a polyhydroxylated compound which stabilizes PdCd4, a protein inhibiting the cellular growth. We have also developed a synthetic approach toward filipin III, an antibiotic and antifungal macrolide, which possesses a 1,3-polyol part and a pentaenic part. Several strategies have been envisaged to construct these fragments, which have been synthesized in a convergent manner. These fragments were then coupled using a diastereoselective aldolisation and we were able to access the complete carbon skeleton of filipin III
Pichon, Christophe. "Valorisation de cyclobutènes : synthèses et utilisations de ligands chiraux, de polyènes et de monomères pour polymérisation par ouverture de cycle par métathèse." Le Mans, 2002. http://cyberdoc.univ-lemans.fr/theses/2002/2002LEMA1001.pdf.
The main contribution of this work is the synthesis of new cyclobutene compounds, and their applications in organic chemistry. The most important part of this work was to elaborate of 12 cyclobutene or cyclobutane ligands Cyclobutene anhydride can be the starting material of their syntheses. In this case, the enzymatic acylation of meso diol was carried out at low temperature. Alternatively some of these ligands can be prepared more easily starting from the cyclobutane diacide wich was subjected to a resolution step. Some of these molecules were used as chiral ligand in asymmetric catalysis. The enantiomeric excesses were up to 89% which showed the interest of these molecules. The second area was the synthesis of 3 dienic monoacetates Then the strategy was applied to the synthesis of trienes by conrotatory thermal ring opening of alkylidcnecyclobutenes. We examined the torquoselectivity of new substituants. Finally, we studied the influence of allylic substituants in ring opening metathesis polymerisation of this type of cyclene. Collaborating with another team, 3 new monomers were prepared and we succeded in preparing an optically active polymer. Throughout this work, we print out the great interest of cyclobutene compound in the field of organic chemistry. We could extend the chiral pool and the knowledge on ring-opening of cvclobutenes either thermally or by metathesis
Soullez, David. "Synthèse et propriétés du 5-bromopenta-2,4-diénal : voie d'accès aux oméga-halogénopolyénals et aux polyènes fonctionnalisés." Rouen, 1994. http://www.theses.fr/1994ROUES065.
Bentoumi, Wissam. "Synthèse de nouveaux systèmes hexatriéniques di- et tri-halogénés : application à la synthèse d’un composé naturel." Rouen, 2008. http://www.theses.fr/2008ROUES030.
In a first part, we accomplished synthesis and purification of a new intermediaire the 1-bromo-6chlorohexa1,3,5-triène. This last was used during the synthesis of natural product from “falcaire commune”. Two ways of synthesis were performed by using chimioselectives cross coupling reactions. In the second part, we developped a synthesis of bromo fluoro trienes, using modified Wittig reactions. This products were obtained in mixture of isomers. A formal synthesis of fluorine analogues of natural product, which has been discribed in the first part, was established
Amans, Dominique. "Obtention d'unités polyéniques : application à la synthèse de composés biologiquement actifs." Paris 6, 2007. http://www.theses.fr/2007PA066277.
Cornil, Johan. "Couplages et hétérocyclisations métallo-catalysés : approche synthétique de la mirabaline." Thesis, Paris 6, 2014. http://www.theses.fr/2014PA066404.
Linear polyenic units are ubiquitous motifs in natural products. Accessing these structures often requires bifunctionalized reagents whose syntheses are sometimes long and tough. We describe in this manuscript a new efficient and fast method of Heck coupling between a alkenyl iodide functionalized with a MIDA boronate group and various olefins to access dienic MIDA boronates. Those stable building blocks have been used for the formation of functionalized polyenes. This strategy has been applied to the synthesis of the pentaenic moiety of the mirabalin, a macrolide isolated from a marine sponge exhibiting an anticancer activity. This manuscript presents the syntheses of the different fragments of mirabaline involved in a synthetic approach developed in collaboration with the Chimie ParisTech team. Apart from polyenic moieties, 1,2-diol, 1,3-diol and 1,3-aminoalcohol units also represent interesting structures. We have developed an ecofriendly cyclization of hydroxylamine ethers, hydroxylamines and linear carbonates on allylic acetates activated by a Lewis acid to access diastereoselectively vinylic isoxazolidines or vinylic cyclic carbonates
Hebbar, Nordine. "Synthèse de chromophores ONL à base de pyrazine et de systèmes hexatriéniques : applications potentielles en optique non linéraire (ONL)." Rouen, 2008. http://www.theses.fr/2008ROUES060.
This thesis work describes the synthesis of new linear chromophores with potential applications in non linear optic. Various original synthetic ways using metalation and cross-coupling reactions allowed to access to numerous compounds with a π-deficient ring (chloropyrazine) substituted with one or two conjugated polyenic chains bearing donor- or withdrawing electron groups. These linear compounds with a push-pull character have a conjugated backbone allowing an important internal electronic charge transfer between the π-deficient pyrazine ring and the electron-donors groups through the hexatrienic chains. The influence of the nature of the multiple bond on the conjugation has been studied by replacement of a double bond by an alkyne linkage. New compounds with a 2,2¢-bipyrazine core, able to induce metal coordination, have been also synthesized. Symmetrical or dissymmetrical structures have been obtained by substitution of the 5 and 5¢ positions by identical or different conjugated polyenic chains
Christin, Orane. "Synthèse totale de l’énacyloxine IIa, un antibiotique d’origine naturelle au mécanisme d’action original." Electronic Thesis or Diss., Université Paris Cité, 2023. http://www.theses.fr/2023UNIP5197.
Isolated in 1982 by Watanabe et al. from soil bacteria Frateuria sp. W-315, enacyloxin IIa is a polyenic antibiotic displaying a strong activity against both Gram-positive and Gram-negative bacteria as well as a slight activity against fungi. This rather complex polyketide consists of a 23 carbons linear chain bearing 6 stereogenic centers, whose one is chlorinated, alongside a conjugated chlorinated penta-ene attached to a cyclohexane with 3 stereogenic centers. The structural complexity of this target induces a high degree of synthetic difficulty involving the synthesis of the fragile polyene unit or the control of the halogenated carbon stereochemistry. Our retrosynthetic plan features the synthesis of fragments A, B and C prior to their assemblage through esterification and aldol reactions. The synthetic strategy developed for fragment C1-C16 relies on a key Pd(II)-catalyzed alkyne chloroallylation, resulting in the selective formation of the (Z)-vinyl chloride, followed by a Pd(II)/Cu(I)-catalyzed alkyne hydrocarbation of allenes and a final 1,2-elimination step to complete the polyenic chain formation. The synthesis of fragment A C1'-C6' relies on a ring closure metathesis, a Pd(0)-catalyzed carbonylation reaction, and a hydrogenation/isomerization one-pot sequence of the acrylate formed to generate the third stereogenic center. On the other hand, fragment C C17-C23 is obtained through a key L-prolinamide-catalyzed '-chlorination of aldehydes, resulting in the stereoselective formation of the desired chlorinated stereogenic center. Finally, the successful assemblage of fragments B and C was achieved through a diastereoselective Mukaiyama aldol reaction, providing access to the C1-C23 skeleton peculiar to the enacyloxin family. This manuscript also presents initial attempts to assemble fragments A and B
Gnonlonfoun, Noukpo. "Synthèse du loliolide et de composés apparentés : utilisation de sels stanneux et mercuriques comme agents de cyclisation électrophile." Tours, 1987. http://www.theses.fr/1987TOUR4013.
Nguyen, Thuy Linh. "Vers la synthèse totale de la mycangimycine, un acide gras polyènique peroxydé, et synthèse d’analogues plus stables et simplifiés." Thesis, Université Paris-Saclay (ComUE), 2016. http://www.theses.fr/2016SACLS542.
The southern pine beetle (Dendroctonus frontalis) ecosystem has been strongly studied because of the economic losses of conifer production in North America. From these researches, it has emerged that this pine beetle possesses a very complex natural associations with trees, fungi, mites. Recently some reports indicated that a bacterian symbiont (Streptomyces sp. SPB74) produces an unprecedent polyene peroxide, named mycangimycin, which plays a role of antifungal and antiparasitic. This molecule is a polyenic fatty acid containing a 3,5-disubstituted 1,2-dioxolane ring which exhibits exceptional antifungal activity against a wide variety of fungi and activities as antimalarial agent against Plasmodium falciparum.In this manuscript, we reported some attempts towards the synthesis of mycangimycin, especially for the formation of 3,5-disubstituted-1,2-dioxolane moiety which could contribute promisingly to many biological activities as antimalarial and antifungal. The first work focused on the synthesis of the 3,5-disubsituted-1,2-dioxolane ring using cyclopropanols as intermediates, through an oxidative ring opening process. As a result of that, some saturated analogues of mycangimycin were prepared in relatively high yield. In the second part of this manuscript, we have developed an available methodology of nucleophile addition to the peroxycarbenium ions derived from Lewis acid-mediated ionization of 3-alkoxy-1,2-dioxolanes providing 3,5-disubstituted-1,2-dioxolane compounds. Various synthetic analogues or intermediates have been evaluated in in vitro in antiparasitic domains
Le, Gallic Yann. "Nouveaux réactifs de polycinylogation de dérivés carbonylés. Application à la synthèse de rétinoïdes." Rouen, 1992. http://www.theses.fr/1992ROUES036.
Villiers, Pierre. "Synthèse d'un nouveau réactif d'hexavinylogation. Réactions de couplage croisé pallado-catalysées sur le 1,6-dibromohexa-1,3,5-triène." Rouen, 1999. http://www.theses.fr/1999ROUES051.
Cahard, Dominique. "Nouvelle méthode d'obtention d'énolates alcalins à partir d'éthers d'énols silylés ou d'acétates d'énols. Réactions d'aldolisation hautement régiosélectives." Rouen, 1994. http://www.theses.fr/1994ROUES035.
Marchand, Nathalie. "Synthèse et réactivité de polyènones à conjugaison croisée possédant une chiralite planaire." Rennes 1, 1996. http://www.theses.fr/1996REN10115.
Clauss, Philippe. "Synthèse d'algorithmes systoliques et implantation optimale en place sur réseaux de processeurs synchrones." Besançon, 1990. http://www.theses.fr/1990BESA2034.
Perro, Adeline. "Synthèse et valorisation de particules colloïdales de morphologie et de fonctionnalité de surface contrôlées." Phd thesis, Université Sciences et Technologies - Bordeaux I, 2006. http://tel.archives-ouvertes.fr/tel-00136549.
Le contrôle du nombre et de la taille des nodules organiques en croissance peut être réalisé via l'ajustement de certains paramètres expérimentaux tels que les caractéristiques physicochimiques de la silice et/ou de la réaction de polymérisation en émulsion. Des colloïdes remarquables par leurs formes (polyèdres réguliers) et par leurs tailles (quelques centaines de nanomètres) ont été obtenus.
Nous avons également synthétisé des nanoparticules dissymétriques ou « Janus », en référence au dieu romain à deux visages. Nous avons pour cela développé deux voies de synthèse, basées sur le masquage partiel d'un des hémisphères de particules minérales suivi d'une étape de fonctionnalisation de surface régiosélective. Ainsi, des dimères hybrides silice/polystyrène, où le nodule polymère sert de masque temporaire du coeur minéral, se sont avérés de bons candidats dans la réalisation de particules « Janus ». Nous avons également exploité une interface liquide/liquide (émulsions de Pickering) pour générer ce type d'objets.
L'étude des propriétés de ces colloïdes en vue de diverses applications telles que la réalisation de cristaux colloïdaux ou de nanostructures multifonctionnelles complexes a été abordée.
Perro-Marre, Adeline. "Synthèse et valorisation de particules colloïdales de morphologie et de fonctionnalité de surface contrôlées." Bordeaux 1, 2006. http://www.theses.fr/2006BOR13251.
Souyris, Jean-Claude. "Etude polarimétrique de dièdres droits et de dièdres à arête elliptique ou hélicoi͏̈dale. Application à la calibration de radars à synthèse d'ouverture et à l'analyse discriminante de cibles canoniques." Toulouse 3, 1992. http://www.theses.fr/1992TOU30179.
Hadji, Makhlouf. "Synthèse de réseaux à composantes connexes unicycliques." Electronic Thesis or Diss., Evry, Institut national des télécommunications, 2009. http://www.theses.fr/2009TELE0012.
In this thesis, we use the polyhedral approach to solve combinatorial problems in telecommunications context. First, we introduce the problem of network design with unicyclic connected components. We recall that without other constraints, our problem is easy to solve, and we propose a study with new technical constraints. We start our study by adding constraints on the size of cycles. We aim to obtain unicyclic components such that the size of each cycle is not lower than a certain p. This problem is NP-Hard. We describe some valid inequalities for the design of unicyclic graphs with girth constraints. The faces induced by these valid inequalities are also studied. Some of them can be separated in polynomial time. A cutting plane algorithm based on these inequalities is implemented to solve the problem. Furthermore, we focus on a Steiner type problem, which consists in partitioning the graph to unicyclic components, such that some given vertices belong to a cycle. We prove then that our problem is easy to solve, and we propose an exact extended formulation and a partial description of the convex hull of the incidence vectors of our Steiner network problem. Polynomial time separation algorithms are described. One of them is a generalization of the Padberg&Rao algorithm to separate blossom inequalities. Other technical constraints are proposed such as degree constraints, a bound of the number of unicyclic components, constraints related to whether some given pairs of vertices belong to the same component or to different components. Finally, we study the spectra of two specified classes of unicyclic graphs
Hadji, Makhlouf. "Synthèse de réseaux à composantes connexes unicycliques." Phd thesis, Université Pierre et Marie Curie - Paris VI, 2009. http://tel.archives-ouvertes.fr/tel-00459860.
Morvan, Antoine. "Utilisation du modèle polyédrique pour la synthèse d'architectures pipelinées." Phd thesis, École normale supérieure de Cachan - ENS Cachan, 2013. http://tel.archives-ouvertes.fr/tel-00913692.