Thèses sur le sujet « Couplage croisé de Stille »
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Audet, Florian. « Development of new access routes to fluorinated building blocks for agrochemical applications ». Electronic Thesis or Diss., Strasbourg, 2024. http://www.theses.fr/2024STRAF002.
Texte intégralFluorine is naturally occurring on Earth in the form of salts, the most notable being calcium fluoride. Over the last decades, has been used in numerous industrial applications, including pharmaceuticals and agrochemicals. Indeed, many active ingredients used in these fields contain at least one fluorine atom, giving them unique properties by modulating their physico-chemical and biological parameters.The objective of this thesis, in partnership with Bayer CropScience, was to develop new ways of accessing fluorinated synthons for agrochemical applications. We started by investigating a cross-electrophile coupling reaction under electrochemical conditions to access the difluoromethylene moiety. N-Polyfluoroalkylation reactions were then developed using sulfuryl fluoride as the key reagent. Finally, a cross-coupling reaction with a new (1-fluorocyclopropyl)metaloid reagent was developed, enabling the direct introduction of this emerging fluorinated group
Amans, Dominique. « Obtention d'unités polyéniques : application à la synthèse de composés biologiquement actifs ». Paris 6, 2007. http://www.theses.fr/2007PA066277.
Texte intégralAwada, Hussein. « Elaboration des matériaux hybrides, organiques/ oxydes métalliques pour le photovoltaique organique ». Thesis, Pau, 2014. http://www.theses.fr/2014PAUU3016/document.
Texte intégralLes performances et la durée de vie des cellules solaires organiques sont fortement dépendantes de la qualité des matériaux de la couche active et des interfaces dans le dispositif. Dans ce manuscrit, nous avons développé des nouveaux matériaux hybrides organiques-inorganiques pour favoriser le contact entre les matériaux donneur/accepteur d’électrons et ainsi faciliter le transfert de charges à travers le dispositif. Tout d'abord, la synthèse de poly(3-hexylthiophène) P3HT fonctionnalisé par le triéthoxysilane a permis le greffage direct (« grafting-onto ») sur des oxydes métalliques. L’analyse des propriétés électro-optiques montre un transfert de charge efficace du polymère aux nanoparticules; ce qui suggère que ces matériaux sont des candidats potentiels pour l'application photovoltaïque. Dans la deuxième partie, nous avons montré pour la première fois, l’élaboration de brosses de polymères dits à faible bande interdite sur des surfaces d’oxydes métalliques par la technique « grafting-through ». Une densité de greffage élevée, un meilleur empilement des chaines de polymères et des propriétés optiques améliorées ont été obtenus grâce à la technique de greffage et aux caractéristiques du polymère greffé. Enfin, des brosses de P3HT ont été élaborées sur la surface d’oxyde d'indium et d’étain (ITO) en tant que couche de transport de trous de cellules solaires organiques. Les performances photovoltaïques ont montré que les monocouches auto-assemblées de P3HT (SAM) peuvent être une alternative au PEDOT: PSS
Medlej, Hussein. « Copolymères à blocs « rigide-rigide » pour les cellules photovoltaïques organiques ». Thesis, Pau, 2011. http://www.theses.fr/2011PAUU3027/document.
Texte intégralThe performances of organic solar cells based on the concept of bulk heterojunction configuration are strongly influenced by the optoelectronic properties of the electron donor polymer. The aim of this thesis was to develop new π-conjugated polymers to allow a better exploitation of the solar spectrum and thus improving the photogeneration of charges. For this,several polythiophene derivatives substituted by phenyl aromatic groups have been synthesized by the GRIM method, note the homopolymer poly[(3-(4-hexylphenyl)thiophene] (P3HPT) and the diblock copolymer poly[3-(4- exylphenyl)thiophene]-block-poly(3- hexylthiophène) (P3HPT-b-P3HT). We also studied a new family of low band gap polymers based on the alternation of electron-rich thiophene and dithieno[3,2-b:2′,3′-d]silole units andelectron-deficient 2,1,3-benzothiadiazole units. After synthesis of the various monomers, alternating copolymers were then obtained by Stille cross-coupling polycondensation. The different synthesized materials were first characterized by thermogravimetric analysis and by differential scanning calorimetry to study their thermal properties. Then, structural(especially XRD and neutron), optical (UV-visible) and morphological (AFM) characterizations were performed. From the obtained results, we were able to evaluate the relation between structures and properties of materials. Finally, photovoltaic cells based on the synthesized polymers were performed and their performances were correlated to material properties
James, Damien. « Développement d'outils organométalliques en vue du transfert de méthyle, application à la synthèse de radiotraceurs pour la TEP ». Thesis, Bordeaux 1, 2009. http://www.theses.fr/2009BOR13900/document.
Texte intégralThe modified Stille cross-coupling developed by Pr. Fouquet’s group was applied to the methylation of nucleosides, dinucleotides and oligonucleotides in order to develop a methodology for labelling aptamers with carbon 11 for the early diagnosis of cancer by PET. This pallado-catalyzed cross-coupling is based on the use of monoorganotin activated by a source of fluoride accelerating the reaction. Initial methodology tests helped to finalize the transfer of methyl group on various nucleosides and a dinucleotide, with reaction conditions compatible with the short half-life of carbon 11 (20.4 min) and the special nature of oligonucleotides. Then, this methodology was applied to oligonucleotide models obtained after incorporation of the most promising nucleosides
Rodriguez, Alain. « Monoorganoétains activés : nouveaux réactifs pour le couplage de Stille ». Bordeaux 1, 1998. http://www.theses.fr/1998BOR10588.
Texte intégralGervais, Bruno. « Synthèse de caerulomycines par réactions de métallation et de couplage croisé en série pyridinique ». Rouen, 1995. http://www.theses.fr/1995ROUES009.
Texte intégralYalcouye, Boubacar. « Synthèse atropo-sélective de la partie biarylique de la (-)-stéganacine via le couplage croisé de Suzuki-Miyaura et le couplage ARYNE ». Thesis, Strasbourg, 2014. http://www.theses.fr/2014STRAF059.
Texte intégralThe interesting biological properties of axially chiral biaryls and the challenge of Csp2-Csp2 bond formation ofthe biaryl motif have aroused keen interest among synthetic organic chemists. The axially chiral biaryls areprivileged structures in medicinal chemistry and in asymmetric catalysis. The goal of our research is based onthe control of the axial chirality of (-)-steganacin using two differents atropo-selective approaches: Suzuki-Miyaura cross-coupling (in presence of transition metals), and ARYNE coupling (without any transitionmetals). The atropo-diastereoselective Suzuki-Miyaura cross-coupling was carried out using enantiopure β-hydroxysulfoxydes as chiral auxiliary. The resulting diastereopure biaryl was converted into an intermediatereported in the literature without any epimerization of axial chirality. The second approach was the atropodiastereoselectiveARYNE coupling which was tested for the first time with the enantiopure p-tolylsulfoxyde.However, we encountered a problem due to lack of reactivity of lithiated arylsulfoxide. Finally, the axialchirality of (-)-steganacin was controlled using oxazolines as chiral auxiliary
Gilles, Pierre. « Couplage croisé induit par SmI2 de nitrones avec des acrylates silylés : synthèse de Pyrrolizidines polyhydroxylées ». Phd thesis, Université de Grenoble, 2011. http://tel.archives-ouvertes.fr/tel-00647130.
Texte intégralRousseau, Lidie. « Catalyse au fer des réactions de couplage croisé : mécanismes, identification et spéciation des intermédiaires réactionnels ». Thesis, université Paris-Saclay, 2020. http://www.theses.fr/2020UPASF020.
Texte intégralFor a few years iron catalysis has been considered as a cheap and environmentally benign alternative for traditional noble metal catalysts. Still, because of its hardly controlled access to a large scope of oxidation and spin states, iron’s reactivity as a catalyst has not been fully understood yet. This work first investigates the question of iron’s catalytically active oxidation states in cross-coupling reactions, through an experimental and computational study. The second part of the manuscript deals with the comprehension of some Fe-catalyzed cross-coupling reactions. The detrimental homocoupling pathway of an aryl-aryl Kumada reaction is elucidated, and the mechanism of the reaction between organomanganese nucleophiles and alkenyl electrophiles is investigated. Finally, the modification of the metal’s coordination sphere thanks to the addition of σ-donating ligands helps to understand the matter of the transmetallation degree control during the cross-coupling process. This work uses classic inorganic chemistry techniques, along with several spectroscopies (NMR, EPR, Mössbauer) and theoretical DFT calculations
Virolleaud, Marie-Alice. « Processus domino de métathèse cyclisante et couplage croisé : application à la synthèse de produits naturels ». Lyon 1, 2006. http://www.theses.fr/2006LYO10174.
Texte intégralCorpet, Martin. « Réactions des arylzinciques avec les dérivés d'alcynes catalysées par le cobalt ». Phd thesis, Ecole Polytechnique X, 2013. http://pastel.archives-ouvertes.fr/pastel-00961703.
Texte intégralThomas, dit Dumont Laurence. « Contribution à la synthèse de la Streptonigrine. Synthèse de 4-phénylpyridines polyfonctionnelles par métallation et couplage croisé ». Rouen, 1992. http://www.theses.fr/1992ROUES045.
Texte intégralVilliers, 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.
Texte intégralDecottignies, Audrey. « Catalyse dans l'eau en présence de cyclodextrine native ou modifiée : Application au couplage croisé de type Suzuki ». Thesis, Compiègne, 2013. http://www.theses.fr/2013COMP2072/document.
Texte intégralFor a few years, the priority task for actors of the chemical field has been the design of greener products and greener chemical processes to meet the environmental concerns. Thus, the twelve principles of the green chemistry were set. One of them is to substitute toxic organic solvents for more eco-compatible solvents, such as water, during chemical synthesis. More generally speaking, catalysis plays a significant role in this green chemistry policy as it enables to enhance energy saving, to reduce the quantity of the used compounds and to reduce as well the separation processes by increasing the selectivity. However, the low solubility of organic substrates in water prevents from having profitable yields. To tackle the issue, the catalysis by inverse phase transfer can be used. Therefore, the synthesis of new water soluble organometallic catalysts was considered. These catalysts will be derivates of cyclodextrin and will allow carrying the substrate in aqueous phase by supramolecular recognition
Berghian-, Groşan Ana Camelia. « Synthèse et stéréochimie de systèmes 3. 7-dioxa-1-azabicyclo[3. 3. 0]octaniques fonctionnalisés : Etude la métallation de bis-diazines et de diazines substituées par des groupements chélatants ». Rouen, 2006. http://www.theses.fr/2006ROUES040.
Texte intégralThis work deals with the synthesis, the stereochemical analysis and functionalisation of compounds bearing the 3. 7-dioxa-r-1-azabicyclo[3. 3. 0]-oct-c-5-ylmethoxy heterocyclic system such as substituent at the α position of a π-deficient system such as (benzo)diazines or s-triazines. The first chapter deals with the bibliography and interest of DOABO heterocycles and diazines. The second chapter presents the synthesis and stereochemistry of a new class of compounds such as α-(3. 7-dioxa-r-1-azabicyclo[3. 3. 0]-oct-c-5-ylmethoxy)-di(s-tri)azines. The stereochemistry of this new series is discussed in terms of conformational chirality of the DOABO system, found different in solution (1H RMND)against solid state (X Ray Diffractometry), meso vs. Chiral forms respectively. The third chapter presents the functionalisation of α-(3. 7-dioxa-r-1-azabicyclo[3. 3. 0]-oct-c-5-ylmethoxy)-(beno)diazines via regioselective Directed ortho-metallation (DoM) reaction using lithiated bases. The fourth chapter describes the synthesis of π-deficient biarylic compounds of type bis(α-methoxy)diazines and 2-pyridyldiazines. They are available by directed ortho-(trans)metallation followed by Negishi or Stille cross-coupling. The functionalisation via metallation of 2-pyridyldiazines occurs on the diazine site, at the ortho-position with respect to Ar-Ar bond
Demange, Matthieu. « Réactivité de complexes de métaux riches : activation de petites molécules, synthèse de nanoparticules et catalyse de couplage croisé ». Phd thesis, Ecole Polytechnique X, 2011. http://pastel.archives-ouvertes.fr/pastel-00720846.
Texte intégralZhou, Edouard. « Nouveaux systèmes catalytiques appliqués aux formations de liaisons C—C par couplage croisé catalysé par des sels de fer : applications, mécanismes ». Thesis, Paris Sciences et Lettres (ComUE), 2018. http://www.theses.fr/2018PSLEC008.
Texte intégralCornec, Anne-Sophie. « Synthèse et relation structure-propriétés photophysiques de nouveaux fluorophores diaziniques obtenus par réactions de couplage croisé et "Click Chemistry" ». Rouen, 2012. http://www.theses.fr/2012ROUES002.
Texte intégralLakmini, Hakim. « Etudes mécanistiques de réactions catalysées par des complexes de palladium mettant en jeu des réactifs organoborés : homocouplage et couplage croisé ». Paris 6, 2006. http://www.theses.fr/2006PA066498.
Texte intégralBennacer, Bibia. « Synthèse de l'éponémycine et analogues à activité anti-angiogénique ». Paris 11, 2002. http://www.theses.fr/2002PA112161.
Texte intégralIn this thesis we describe on the one hand a strategy for the enantiospecific synthesis of (S)-γ,delta-didehydroleucine, an unnatural amino acid present in the peptide epoxide eponemycin. In this context, we made use of the diastereoselective alkylation method developed by Myers employing pseudoephedrine as the chiral auxiliary. This process appears to be a powerful tool for the construction of eponemycin analogues. For instance, the diastereoselective alkylation of pseudoephedrine glycinamide with 3-bromo-2-methylpropene followed by the amide attack by a furyllithium derivative gave furane intermediates. Subsequent peptide coupling with (2S)-N- (6-methylheptanoyl)serine provides access to diverse eponemycin analogues. In the course of this work, we also perfected a new route for the synthesis of 6,7-dihydroeponermycin, a saturated derivative of eponemycin, which displays the same antiangenic properties. This component will be used as a reference for the evaluation of the biological activities of the different analogues. The principal difficulty was the synthesis of 6. 7-dihydroeponemycin right-hand side composed of a leucine moiety and a highly sensitive α-hydroxymethyl epoxyketone motif. This was achieved by coupling Fmoc-leucine acid chloride with tributylvinyltin under Stille conditions followed with a Baylis-Hillman type reaction to give the α-hydroxymethylenone. Epoxidation of this enone with Triton B® and coupling with (2S)-N-(6-methylheptanoyl)serine finally furnished the desired 6,7-dihydroeponemycin optically pure
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.
Texte intégralIn 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
Buron, Frédéric. « Etude de complexes « ates » en série diazinique : Synthèse de molécules biologiquement actives à cœur pyrazinique ». Rouen, 2006. http://www.theses.fr/2006ROUES020.
Texte intégralIn a first part, we developed a new methodology of synthesis in the diazine series by carrying out the Metal Halogene Exchange by the use of n-Butyl Lithium Magnesate. In the second part, we proposed to synthesize Barrenazines by pyrazinic ring formation from the (L)-aspartic acid and we could synthesize a precursor of Barrenazine A. We synthesized natural products extracted from ascidies : Botryllazines A and B which present cytotoxic properties. Our synthetic strategy is based on the pyrazinic ring fonctionnalisation by using metalation and cross coupling reactions. We have synthesized Botryllazine A and B as well as an isomer of Botryllazine A
Brückner, Sébastien. « Mise en évidence d'une réaction tandem Stille/cycloaddition [4+2] : Application à la synthèse de nouveaux systèmes pentacycliques stéroi͏̈diens et étude mécanistique ». Université Louis Pasteur (Strasbourg) (1971-2008), 2002. http://www.theses.fr/2002STR13123.
Texte intégralIn order to synthesize thirteen membered macrocycles, we developed a strategy based on the differentiated reactivity of the two enoltriflate moieties of bis(enoltrifluoromethanesulfonates). This strategy involving palladium catalysed coupling reactions allowed the synthesis of polyunsaturated and stannylated derivatives. Instead of the expected macrocycles, the macrocyclization of these precursors leads, at room temperature, to several pentacyclic structures by a Stille/ [4+2] cycloaddition tandem reaction. This kind of structure is present in the xestobergsterol, a cytotoxic natural compound. Therefore we used this key step to synthesize other polysubstituted pentacyclic systems. Since this type of mild cyclization has no precedent in the literature, we investigated a mechanistic study. Due to several considerations and synthesises we postulated a palladium catalyzed mechanism which has to be proven
Moncomble, Aurélien, et Corinne Gosmini. « Étude théorique et expérimentale de la formation de quelques liaisons carbone-carbone par catalyse au cobalt à partir d'halogénures aromatiques ». Phd thesis, Ecole Polytechnique X, 2010. http://pastel.archives-ouvertes.fr/pastel-00569164.
Texte intégralBegouin, Jeanne-Marie. « Activation de composés aromatiques et hétéroaromatiques pour la formation de liaisons C-C et C-N par catalyse au cobalt ». Thesis, Paris Est, 2009. http://www.theses.fr/2009PEST0033.
Texte intégralTransition metal-catalyzed cross-coupling reactions allowing the formation of C-C or C-Heteroatom bonds underlie the synthesis of key intermediates for pharmaceutical, supramolecular chemistry and material sciences. Thereby, the development of these methodologies is prominent and an increasing number of studies are devoted to these processes. However, some metallic catalysts are known to be rather expensive or toxic. Consequently, the development of alternative sustainable catalysts such as cobalt or ironbased catalysts has been studied over the past few years. Cobalt-catalysts have been little-used although they have shown to be effective for various C-C bond forming reactions. Functionalized arylzinc reagents can be readily obtained from the corresponding arylhalides using a CoBr2-catalyzed reaction. First we envisioned using these arylzinc reagents in CoBr2-catalyzed cross-coupling reactions with chlorodiazines and chlorotriazines leading to aryldiazines and aryltriazines. Benzylzinc reagents had also been used in these reactions and we synthesized various benzyltriazines in this manner. We also studied whether we can use other kind of substrates in these reactions. Thus, we performed CoBr2-catalyzed cross-coupling reactions between arylzinc reagents and methylthiopyrimidines or methylthiobenzo[b]thiazole derivatives leading to 2,4-diarylpyrimidines and 2- arylbenzo[b]thiazole. Then, we studied the reactivity of benzonitrile derivatives in direct cross-coupling reactions with arylhalide based on C-CN bond activation using CoBr2 as catalyst. Finally, we also carried out the study of CoBr2-catalyzed C-N cross-coupling reactions for the synthesis of diarylamines
Rocca, Patrick. « Nouvelle synthèse d'aza-carbazoles par association des réactions de métallation et de couplage croisé hétéro-aromatique. Préparation d'alcaloïdes de la famille des béta-carbolines ». Rouen, 1992. http://www.theses.fr/1992ROUES037.
Texte intégralRouchet, Jean-Baptiste. « Etude de couplages croisés directs catalytiques décarboxylants d'acides picoliniques et cinnamiques ». Thesis, Rouen, INSA, 2015. http://www.theses.fr/2015ISAM0019/document.
Texte intégralThe functionalization of heterocycles arouse an interest both in supramolecular chemistry and in pharmaceuticals. Based on the so-called concept better with less, the development of direct functionalization methodologies of heterocycles involving C–H and C–CO₂H bonds has emerged as an efficient, modern alternative and complementary process to traditional cross coupling methods, avoiding thus the use of stoichiometric organometallic reagents that are often air and moisture sensitive. In this context, the aim of this PhD work was to develop new decarboxylative cross couplings, CO₂H / C-X and CO₂H / C−H, using substituted 2-carboxyazine N-oxides and α-methoxyacrylic acids as new coupling partners.The first part of this work has been focused on the development of the versatile Pd-catalyzed and Ag-assisted decarboxylative coupling of quinaldic and picolonic acids N-oxides as well as 3-carboxyisoquinoline acids with (hetero)aryl halides. Although copper (I) appeared to be more efficient by DFT calculations to perform ipsodecarboxylation-metallation step, only silver catalysis revealed to be much more adequate to achieve the conventional decarboxylative coupling and this was then pointed out with the high regioselectivity observed at the carboxy function site. This reaction showed a large reactivity spectrum and tolerated for the first time substituents on azinic core. It is also a synthetic alternative to the direct C−H arylation on azine N-oxides for the regioselective synthesis of 2-arylated substituted pyridines and 3-arylated isoquinolines. As application, a modular and flexible approach has been developed for the synthesis of the highly functionalized 1,3-substitute disoquinoline 5, shown as an antitumor agent.In the second part, the first Pd-catalyzed and Cu-assisted decarboxylative / C-H alkenylation of heterocycleswith various α−methoxyacrylic acids was reported offering general stereocontrolled access to heteroarylated enol ethers in geminal position. The direct introduction of vinyl ether allows to expand the panel of C-H bond functionalizations methodologies of heterocycles. The high potential for subsequent post-functional adjustment of the vinyl ether moiety enable thus the synthesis of heteroarylated α,β-enolizable ketones and polysusbituted alkenes
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.
Texte intégralThis 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
Mongin, Florence. « Régiosélectivité des réactions de bromation, d'échange halogène-métal et de couplage croisé sur des dérivés de la 8-hydroxyquinoléine. Application à la synthèse de pyridocarbazoles ». Rouen, 1994. http://www.theses.fr/1994ROUES063.
Texte intégralRérat, Alice. « Couplages croisés catalysés au cobalt entre des arylzinciques et divers substrats électrophiles ». Thesis, Université Paris-Saclay (ComUE), 2016. http://www.theses.fr/2016SACLX066/document.
Texte intégralThis thesis presents new cobaltcatalyzed cross-coupling reactions between arylzinc derivatives and various electrophilic reagents. After a general introduction on cobalt-catalysis and arylzinc compounds, the first chapter is dealing with the formation of diaryl ketones. Reaction between arylzinc bromides and ethyl chloroformate in presence of cobalt bromide and bipyridine ligand leads to the formation of symmetrical diaryl ketones with very good yields under simple conditions. It has been shown that ethyl chloroformate decomposes into carbon monoxide during the reaction. First attempts to extend this method to the synthesis of unsymetrical diaryl ketones are also described from arylzinc bromides and various carbonyl containing substrates. As for the second chapter, it is focused on the Negishi coupling between arylzinc bromides and an aryl bromide or an heteroaryl chloride. The advantage of this method is that the cobalt used to form the arylzinc bromide also serves to form the biaryl, hence there is no addition of another catalyst in the second step of the reaction. Results about the formation of biaryls are promising, but this reaction needs to be thorough. A similar methodology was used for the synthesis of new delayed fluorescence molecules to obtain highly efficient organic light emitting diodes. The third chapter describes the cobalt-catalyzed reaction between an arylzinc bromide and an electrophilic source of sulfur, a Bunte salt. However, these aryl sulfides can be easily oxidized in the reaction mixture and give sulfoxides and sulfones, which limit the use of this method. Finally, the last chapter is about preliminary works on the trifluoromethylation of arylzinc bromides from electrophilic or nucleophilic trifluoromethyl sources
Carella, Alexandre. « Conception et synthèse de la partie active d'un moteur moléculaire rotatif ». Toulouse 3, 2004. http://www.theses.fr/2004TOU30123.
Texte intégralIn the field of nanosciences, the conception and the construction of a molecular motor at the nanometric scale is a conceptual and synthetic challenge. A molecular motor is a molecule which can transform energy into an unidirectional movement. We decided to synthesized a molecular motor electrically addressed, designed to be studied as a single molecules between the electrodes of a nanojunction by near field microscopy. It will be a ruthenium organometallic complex bearing two different ligands which would act as a rotor and a stator. The stator is an hydrotrisindazolylborate ligand with a tripodal shape which have been functionalized to interact strongly with oxide surface currently used in AFM experiments. The rotor is a cyclopentadienyl ligand connected to five electroactive group by linear and rigid arms. Electroactive group will transfer electrons from the cathode to the anode and convert the electrical energy into an rotational motion of the rotor
Oertel, Anna Magdalena. « Synthèse et réactivité de complexes du nickel(II) comportant des ligands carbène N-hétérocyclique : des réactions de couplage C-C croisé à l'activation de liaisons C-H ». Strasbourg, 2010. https://publication-theses.unistra.fr/public/theses_doctorat/2010/OERTEL_Anna_Magdalena_2010.pdf.
Texte intégralThe research in this thesis targets some aspects of the chemistry of nickel-N-heterocyclic carbene (NHC) complexes. A series of half-sandwich nickel(II) complexes, [Ni(R-NHC-n-Bu]XCp†] (Cp† = Cp, Cp*, X = Cl, I), bearing a N-bound n-butyl sidearm NHC ligands has been synthesized from the appropriate imidazolium halides and nickelocene or [Ni(acac)Cp*] as models for heterogenized versions of these complexes. All these complexes were fully characterized by standard spectroscopic techniques [1H and 13C{1H}NMR spectroscopy, 2D spectroscopy when appropriate, MS, and elemental analyses]. Furthermore, many representative complexes were the subject of single-crystal X-ray diffraction studies. All these complexes feature a two-legged piano stool geometry common for 18-electron MCp†L2 compounds with a trigonal planar geometry around the central nickel atom. The [Ni(Ar-NHC-n-Bu)ICp] compounds are highly active catalysts for the Suzuki cross-coupling of aryl bromides or chlorides with phenylboronic acid in the absence of any reductant or co-catalyst and show higher turnover frequencies (TOF) than seen in their closely related symmetric [Ni(Ar2-NHC)LCp†] counterparts. The origin of the improved stability of the in situ generated active species is discussed. A heterogenized version of these complexes onto alumina has been prepared by employing 3-(trialkoxysilylpropyl)imidazolium halides and tested in Suzuki cross-coupling. In the prospect of enhancing the longevity of the active species, unprecedented half-sandwich Ni(II) complexes bearing two different NHC ligands were prepared by displacement of the labile acetonitrile ligand from [Ni(Ar2-NHC)(CH3CN)Cp]+X- with a “free” NHC. The resulting cationic bis-(NHC)-nickel complexes [Ni(NHC)(NHC’)Cp]+X- show remarkable stability, and thus low acitivity in Suzuki couplings. The Ni– NHC bonds are particularly robust as can be demonstrated by the displacement of the Cp, and not of a NHC ligand, when these bis-NHC Cp complexes are protonated. The final chapter presents a novel reaction in which the base-promoted activation of sp3-hybridized C– H bonds a- to functional organic groups at Cp†Ni-NHC centres was achieved. The scope and breadth of this activation is demonstrated by the activation of acetonitrile, acetone and other ketones under relatively mild conditions to give a range of new nickel alkyls. A remarkable double activation of acetone was notably demonstrated. The activation of C–H bonds a-to nitriles in NHC-attached sidearms to give a series of new half-sandwich nickelacycles was also achieved. Possible mechanistic pathways for these reactions have been the subject of theoretical DFT analyses. Similarly to the bis-NHC species, the nickelacycles show great robustness of the NHC– and alkyl–Ni bonds
Célanire, Sylvain. « Synthèse de cyclohexa[a]quinolizidines et de cyclohexa[a]indolizidines, analogues tricycliques de 8-azasteroïdes. Nouvelle synthèse d'une cyclopenta[b]pyridinone par des réactions de couplage croisé ». Rouen, 1999. http://www.theses.fr/1999ROUES062.
Texte intégralLefoix, Myriam. « Synthèse de 5-azaindolocarbazoles.Evaluation de leur activité antitumorale ». Phd thesis, Université d'Orléans, 2005. http://tel.archives-ouvertes.fr/tel-00148832.
Texte intégralprogresse, afin de développer de nouveaux composés plus spécifiques, diminuant les effets
secondaires et les phénomènes de résistance. Les indolocarbazoles, molécules naturelles aux
propriétés antitumorales, représentent un outil de choix pour cette thérapie. Les
modifications réalisées sur ce squelette, à savoir le remplacement d'une sous-structure
indolique par un 5-azaindole, ont permis de synthétiser des 5-azaindolocarbazoles.
Une étude approfondie de la réactivité du 5-azaindole a été nécessaire. La fonctionnalisation
des sommets 2 ou 3, réalisée au cours de diverses réactions, autorise la synthèse de composés
plus complexes. Elle a déjà permis d'accéder aux différents 5-azaindolocarbazoles ciblés. Les
activités biologiques, particulièrement intéressantes, sont également rapportées dans le
document.
Pham, Phuoc Dien. « Synthèses et utilisations de réactifs à base d'étain supportés sur liquide ionique ». Le Mans, 2009. http://cyberdoc.univ-lemans.fr/theses/2009/2009LEMA1020.pdf.
Texte intégralTriorganotin derivatives display reat potential as reagents for organic and radical chemistry but their use has been avoided for the synthesis of pharmacologically active substances due to their toxicity and the difficulties of removing tin residues from the products. Efforts to overcome these problems have been made : supporting the triorganotin reagents on an ionic liquid in order to minimize the contamination of the products with tin. Moreover, a simple work-up procedure (extraction, filtration, or distillation) has been also developed thanks to the immobilization of tin reagents on an ionic liquid. New ionic liquid supported tin reagents were synthesized and were applied in 3 fields as follows: 1. Stille cross coupling reactions: High yields of biaryl (Sn residue < 6 ppm) from iodoaryl were obtained under low temperature(35 °C), solvent-free, ligand-free conditions and simple purification techniques (by extraction). Moreover, the tin compound could be recycled up to 5 times without significant loss of reactivity. 2. Catalytic free radical reduction: A variety of alkyl and aryl halides can be reduced in excellent yields (Sn residue was 5–8 ppm) with high selectivity (alkyl vs aryl) to afford the desired products with a simple work-up procedure. The products were easily isolated by a simple filtration step. 3. Solvent-Free Direct Reductive Amination: An organotin reagent supported on an ionic liquid was used as a catalytic reductant (0. 1 mol%) for the solvent-free direct reductive amination of aldehydes and ketones. A convenient work-up procedure (by distillation) has been developed for a wide variety of substrates. This method presents many advantages as the solvent-free reaction conditions and catalytic quantities of highly reactive organotin reagent used facilitate the purification of products, thus minimizing the contamination of the product by tin (Sn residue was 1. 7–2. 5 ppm)
Gonnard, Laurine. « Réactions métallo-catalysées : synthèse d'hétérocycles azotés saturés fonctionnalisés ». Thesis, Paris 6, 2017. http://www.theses.fr/2017PA066438/document.
Texte intégralIn order to facilitate the total synthesis of active molecules used in pharmaceutical or agrochemical industries, chemists try constantly to develop new, general, practical and sustainable methods. In 2014, a study revealed that piperidine was the most frequently present aza-heterocycle in medicines approved by the Food and Drug Administration (FDA). In this context, three different methods were developed during this Ph.D in order to synthesize functionalized piperidines. A wide variety of substituted piperidines was first efficiently obtained by a cobalt catalyzed cross-coupling reaction between 4- and 3-halogenopiperidines and Grignard reagents. Cobalt has appeared as a good alternative to the expensive palladium salts or the toxic nickel salts. Moreover, it can prevent side reactions such as dehydrohalogenation or β-H elimination. Next, 2-dienylpiperidines, present in a myriad of alkaloids, were prepared by iron catalyzed cyclization from diallylic amino-alcools. Finally, new conditions for the ruthenium catalyzed C(sp3)‒H monoarylation of piperidines were developed. The influence of the electronic and steric properties of the directing group attached to the nitrogen of the piperidine was fully studied. These methods were then applied to the synthesis of other azacycles
Bourne, branchu Yann. « Complexes de cobalt à ligand N-hétérocyclique pour la catalyse ». Thesis, Université Paris-Saclay (ComUE), 2018. http://www.theses.fr/2018SACLX075/document.
Texte intégralThis thesis is divided in two distinct part: on one side, the works concerning the cobalt insertion into the C(O)–N bond of non-planar amides, and the resulting reactions, and on the other side, the development of a new family of cobalt complexes, based on the 5-(4-pyridyl)dipyrromethene ligand and its derivatives.In the first part, concerning cobalt catalysis with amide derivatives, the reactivity of different cobalt precursors and complexes toward non-planar amides has been studied. The insertion of the cobalt can be realized in presence of bipyridine as ligand, en DMF, with manganese powder as reductant system. The otpimization of the amide-to-ester conversion and the reductive cross-coupling between amides and iodo-aryl is then described.In the second part, concerning the coordination chemistry of cobalt, the development of cobalt-dipyrromethene complexes is presented. Firstly, the optimization of the 5-(4-pyridyl)dipyrromethene synthesis is described,followed by complexation tests with different cobalt precursors. With two coordination sites on the ligand, the selective coordination of a transition metal on one of the sites depends mainly on the dipyrrin hindrance. If this part is hindered enough, cobalt chelate preferentially on the pyridyl part. To force the cobalt coordination on the dipyrrin part, it is necessary to occupied the pyridyl part. By coordinating a photoensitive ruthenium precursor on the pyridine, it is possible to obtain un bimetallic cobalt-ruthenium complex, allowing the cobalt photoreduction, and potentially the development of a cobalt catalysis without metallic reductant
Salanouve, Elise. « Complexes de métaux non-nobles de fer et de nickel portant des ligands redox non-innocents et leurs applications en catalyse : de l'activation C-H aux réactions de couplages croisés ». Thesis, Paris 6, 2014. http://www.theses.fr/2014PA066620/document.
Texte intégralThis PhD work has focused on the development of complexes of non-noble metals bearing non-innocent ligands and their catalytic applications as efficient alternatives to noble metal complexes, in the light of increasing concerns regarding cost and sustainability-related issues of noble metals. Towards this goal, we have developed and characterized complexes of non-noble metals (Fe, Ni) with non-innocent ligands using multiple spectroscopic techniques. This work was aimed at broadening the field of useful catalytic applications of these particular complexes. For our dedicated program in iron catalysis, a new method for tandem C–H activation/arylation of unactivated arenes catalyzed by iron complexes bearing redox-active bis(imino)pyridine ligands was developed. Preliminary mechanistic insights were gained based on combined spectroscopic data (NMR, in situ IR, EPR), reactivity studies as well as DFT calculations. The results obtained are clearly in favor of a mechanism distinct to that previously reported for iron-based catalytic systems and are not compatible with homolytic aromatic substitution (HAS). We have also focused on another challenging field in catalysis: cross-coupling reactions catalyzed by nickel as base metal, bearing redox non-innocent ligands. Several challenges in cross-coupling reactions remain among which coupling of non-activated alkyl halides. Mechanisms involving nickel catalysts often differ from those involved in palladium catalyzed cross-coupling reactions. The behavior of nickel complexes bearing redox non-innocent ligands was studied in order to unveil new reactivites and gain a better understanding of the catalytic cycles at stake
Godebout, Virginie. « Les Ethers d'énols β-bromés chiraux : synthèse et propriétés ». Rouen, 1998. http://www.theses.fr/1998ROUES035.
Texte intégralNeouchy, Zeïna. « Couplage croisé d’éthers d’énol méthyliques par activation de liaisons C(sp2)-OCH3 catalysée par le nickel et Synthèse d’amines α-trifluorométhylées acycliques optiquement activespar réarrangement de β-aminoalcools α-trifluorométhylés ». Thesis, Paris Sciences et Lettres (ComUE), 2018. http://www.theses.fr/2018PSLET016.
Texte intégralIn organic chemistry, the development of robust and sustainable synthetic methods has always been a challenge. Moreover, in medicinal chemistry, the development of fluorinated building blocks synthetic methods with high value is important to access bioactive compounds. In this manuscript, we report efficient and easy to carry methods for the formation of carbon-carbon bonds catalyzed by nickel and the formation of carbon-heteroatom bonds by a rearrangement of α-trifluoromethyl-β aminoalcools.We demonstrated that it is possible to perform a cross-coupling reaction of an alkenyl methy ether with a Grignard reagent using a simple catalytic system based on Ni(OAc)2/(O)PPh3 under mild conditions (40°C) via the insertion of nickel into C-OMe bond. This method has been applied to the synthesis of an antitumoral agent, DMU-212.The synthesis of enantioenriched linear α-trifluoromethylamine derivatives is reported consisting in a rearrangement of α-trifluoromethyl-β aminoalcool based on an established strategy in our group via an aziridinium intermediate. We have shown that the synthesized compounds can be involved in post-functionalization reactions
Barré, Baptiste. « Fonctionnalisation d'hétérocycles par des réactions métallo-catalysées ». Thesis, Paris 6, 2016. http://www.theses.fr/2016PA066461.
Texte intégralCross-coupling reactions, as Prof. K. C. Nicolaou said “have changed the way we think about synthesis”. Indeed, cross-coupling reactions are powerful tools to access easily and rapidly to a library of compounds in the context of medicinal chemistry. Palladium-catalysed cross-coupling rules the field and was recognized by the Nobel Prize in 2010 but, since its discovery, others metals have appeared as good alternatives to the expensive and toxic palladium salts such as copper, nickel, cobalt and iron salts. In medicinal chemistry, heterocycles are essential moieties since they are found in a great number of drugs on the market. It is always a challenge for organic chemists to develop new methods to produce motifs with interesting pharmacological properties such as substituted azetidines, pyrrolidines and oxetanes. sp3 Halides are challenging substrates for cross-coupling because the oxidative addition of the metal in the C-X bond is difficult and because side reactions can take place like -hydride elimination or dehydrohalogenation. Nevertheless, cobalt and iron are suitable catalysts to perform cross-coupling reactions on sp3 halides. Herein, we would like to report two catalytic systems allowing the cross-coupling between heterocyclic alkyl halides and Grignard reagents using cobalt and iron salts. A mechanistic study on cobalt-catalysed cross-coupling reaction between halides and Grignard reagents will be also presented
Dikova, Anna. « Des nosylates à la synthèse totale de diènediynes ». Thesis, Strasbourg, 2016. http://www.theses.fr/2016STRAF036/document.
Texte intégralThe total synthesis of N1999-A2 is a synthetic challenge which mobilized several renown groups specialized in this field. Our group is also interested in the construction of this complex molecule. Our strategy is based on the know-how of our laboratory. The considered synthetic approach permits the formation of the dienediyne core at the lasts steps of the synthesis. We managed to achieve the first coupling of the two key building blocks. This is a major advance in our synthetic approach. This project also allowed the development of new synthetic methodologies. In particular the palladium catalyzed cross-coupling reactions with aryl and vinyl nosylates, novel stable and reactive electrophilic partners. This discovery will allow us to bypass the extreme instability of several key intermediates (enol triflates)
Pineau, Philippe. « Nouvelles voies de synthèse de dérivés de substitution de l'ellipticine : valorisation de la métallation de pyridine ». Rouen, 1989. http://www.theses.fr/1989ROUES037.
Texte intégralKerric, Gaëlle. « Synthèse et caractérisation de nouveaux organostanniques sur support solide : utilisation en synthèse organique ». Nantes, 2010. http://www.theses.fr/2010NANT2109.
Texte intégralPolymer-supported organotins are convenient reagents to achieve organic synthesis and to circumvent problems due to pollution by tin residues. First, we studied the reactivity and the recycling of a polymer-supported phenyltin reagent towards Stille cross-coupling. The low levels of tin and palladium in the cross-coupling products prompted us to synthesize other supported aryl-and heteroaryltins. In a second part, new functionalized grafted vinyl-, alcynyl-, allyltins were prepared and fully characterized by NMR HRMAS. These reagents were efficiently used in Stille cross-coupling for supported vinyltins and in the allylation of benzaldehyde for supported allyltins. Last, a new route to 5-substituted-1H-tetrazoles was developed by using alkoxy organotins. This work exhibits the advantages of the solid-phase methodology namely its easy workup, which allows a very low level of tin contamination in the final products and the easy recycling of the polymer-supported organotin reagents
D'accriscio, Florian. « Complexes de nickel caméléons : exploration de tous ses degrès d'oxydation pour la formation de liaisons C-C et C-CF3 ». Thesis, Toulouse 3, 2017. http://www.theses.fr/2017TOU30216.
Texte intégralThis research project aims at the study of nickel complexes in different oxidation states (from 0 to +IV) in order to promote C–C and C–CF3 bond formation. In a first part, low-valent nickel complexes are used as catalysts to perform Negishi and Suzuki-Miyaura cross-coupling reactions. If the C–C bond formation is a well-known reaction using palladium catalysts, the use of nickel complexes as catalysts is more complicated to understand in the mechanistic aspect. In this work, the key point is the use of a bis-phosphine ligand which allows the synthesis and isolation of nickel(0) complexes. A full mechanistic study via stoichiometric reactions as well as DFT calculations confirms that the Negishi cross-coupling works only on a Ni(0)/Ni(II) catalytic cycle. Surprisingly, preliminary studies on the Suzuki-Miyaura cross-coupling reactions show that the mechanism pathway is completely different. In a second part, our interest is focused on the C–CF3 bond formation using high-valent nickel complexes. In chemical industries, the C–CF3 bond formation requires harsh conditions and also produces toxic waste for the environment. This mainly explains why the use of transition metals is still challenging in this topic. However in the last few years, the interest for the use of nickel complexes as coupling agent for C–CF3 bond formation has grown. This work deals with the synthesis of nickel(III) complexes bearing two CF3 substituents and the use of a dimeric nickel(III) complex as a building block for the formation [NiIII(CF3)2] type complexes. If these species do not promote the C–CF3 cross coupling, a nickel(IV) complex shows its ability to create this bond. Moreover, this is the first nickel(IV) species bearing both fluorine and CF3 substituents at the same metal center and promoting C–H bond activation
BUFFNOIR, STEPHANE. « Synthese et marquage de flavonoides mettant en jeu la chimie organometallique - synthese de la prenylcatechine et acces aux dimeres de flavonoides - activation du couplage de stille par l'ion fluorure - marquages de la catechine et de l'epicatechine ». Paris 6, 1998. http://www.theses.fr/1998PA066050.
Texte intégralLévêque, Christophe. « Photooxydation de silicates hypercoordinés pour la génération de radicaux carbonés : processus radicalaires et catalyse duale ». Thesis, Paris 6, 2017. http://www.theses.fr/2017PA066209.
Texte intégralPhotoredox catalysis in visible light has succeeded in establishing itself as a gentle and eco-compatible method of formation of radical species, and more particularly of carbon radicals. Although this catalysis has proved to be efficient for the formation of carbon-carbon/heteroatom bonds, the generated carbon centered radicals are oftenverystabilized.Conversely, bis-catecholato silicates have shown to be capable of generating alkyl radicals that are not stabilized by photooxidation using polypyridine complexes of transition metals (Ru, Ir) that are photoactive in visible light but also organic photocatalysts. The radicals formed can thus be trapped by various radical acceptors. In addition, the bis-catecholato silicates can be employed in cross-coupling reactions with alkene halides and (hetero)aromatic halides under photoredox/nickel dual catalysis conditions for the formation of C(sp2) – C(sp3) bonds. The methodology can also be extended to C(sp3) – C (sp3) with some limitations. On the other hand, a study comparing the silicates and the "ate-complex" of boron for the formation of radicals by oxidation process is presented. Finally, promising works on the oxidation of silicates by copper complexes bearing non-innocent ligands have been initiated
Rosa, Lourenço de Pina Cardoso Bernardo. « Structure of cationic CNHC,Calkyl nickelacycles and their activity in the catalytic functionalization of the C–H bonds of azoles ». Thesis, Strasbourg, 2018. http://www.theses.fr/2018STRAF033/document.
Texte intégralThis thesis develops the study of nickel(II) complexes bearing N-heterocyclic carbene ligands (NHC) in two axes: the synthesis and characterization of nickelacyclic complexes with a carbon-carbon chelating ligand (CNHC,Calkyl); and their catalytic activity in the construction of carbon-carbon bonds (Csp2–Csp2/Csp3) of 1-chalcogene-azoles by carbon-hydrogen (C–H) bond functionalization. A series of cationic CNHC,Calkyl-Ni(II) metallacyclic acetonitrile adducts was synthetized by the removal of a cyclopentadienyl ligand from parent 18 valence electron half-sandwich nickelacycles. The cationic complexes were determined to exist as rare coordinatively and electronically unsaturated T-shaped 14 valence electron Ni(II) species, in the solid state. Application of these new complexes to the cross-coupling of benzothiazole with iodoarenes proved to be a successful strategy in Csp2–Csp2 bond formation, by the combination of a stabilizing metallacyclic scaffold with labile ligands. The discovery of a half-sandwich Ni(II)-(NHC)-(benzothiazolyl) species, inactive in the arylation of benzothiazole, but active for the cross-coupling of benzothiazole with iodoalkanes shows the first example of benzothiazole Csp2–Csp3 bond construction with a Ni(II)-NHC catalyst
Fradon, Alexis. « Design de polymères conjugués pour des applications dans le photovoltaïque assisté par modélisation moléculaire ». Thesis, Bordeaux, 2016. http://www.theses.fr/2016BORD0310/document.
Texte intégralDuring the last decade, a new kind of donor polymers for photovoltaic application have been intensively studied, the low band-gap polymers. They are based on repeating units associating two different moieties, one electron-rich (ER) and one electron-poor (EP), which allow to finely tune the molecular orbitals and to induce a delocalization of the exciton generated upon the photo-excitation process. A large variety of devices are based on such low band-gap polymers, with a power conversion efficiency record around 10%, and, to increase the efficiency, it is necessary to have a better understanding of these polymers during the photo-absorption phenomenon. Computational chemistry isa powerful tool that permits to predict different opto-electronic properties. For this work, we used Density Functional Theory and Time-Dependent Density Functional Theory to compute the optical properties of increasingly large oligomers involving various ER and EP subunits. The optical properties in the polymer limit were then estimated for the different systems by using an extrapolation scheme based on the Kuhn equation. This theoretical screening allowed us to select promising candidates based on benzodithiophene, benzothiadiazole and benzofurazan for syntheses, which were performed by a Stille coupling. The obtained polymers and size-controlled oligomers were further characterized by UV visible spectroscopy, fluorescence, size exclusion chromatography and NMR, in order to extractstructure-properties relationships and correlate experimental results to theoretical data