Dissertationen zum Thema „Catalyse or“
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Nguyen, Thi Xuan Phuong. „La catalyse hétérogène“. Paris 5, 1994. http://www.theses.fr/1994PA05P039.
Der volle Inhalt der QuelleRoudier, Mylène. „Catalyse duale pour une synthèse énantiosélective éco-compatible“. Electronic Thesis or Diss., Aix-Marseille, 2016. http://www.theses.fr/2016AIXM4347.
Der volle Inhalt der QuelleThis manuscript is focus on the development of multicatalyzed reactions involving iminium activation and reversible neutral hydrogen transfer reaction for the synthesis of complexe enantioenriched building blocks from allyl alcohols and 1,3-dicarbonyls.An unprecedented cascade catalysis combining an iron catalyst and a pyrrolidine-base catalyst is developed for the preparation of g-fonctionalized enantioenriched alcohols in a formal redox-, atom- and step-economical approach. The efficiency of this method involving a dual catalysis and a retro-Claisen xas further demonstrated in the short synthesis of several key fragments of biologically active natural products or odorant molecule. This methodolgy was then incremented by a experimental mechanistic study allowing a better understanding of the mechanism of this transformation and leading to a new catalytic systeminvolving three different catalysts (iron complex, copper and organocatalyst). Then, we focused on the development of a new synthetic approach to enantioenriched medium-sized lactones. This methodology is based on a 1,4-Michael addition of cycloalkane-1,3-diones to a,b-insaturated aldehydes. Then, a key chemoselective reductively triggered Claisen fragmentation occurred to generate desired lactones in a rapid manner.Finally, thanks to our methodology developed during this thesis, the total synthesis of floribundane B was studied
Sierra, salazar Andrés Felipe. „Waterborne catalytic materials with original design“. Thesis, Montpellier, Ecole nationale supérieure de chimie, 2017. http://www.theses.fr/2017ENCM0014/document.
Der volle Inhalt der QuelleLa catalyse est l'un des piliers pour le développement de procédés durables, car elle permet d'utiliser moins de ressources en accélérant les réactions chimiques. Afin de fournir des catalyseurs plus performants, cette étude propose une nouvelle méthode de préparation de catalyseurs pour contrôler la distribution de nanoparticules (NPs) métalliques au sein des catalyseurs hiérarchiquement poreux (méso et macro) en combinant la synthèse de latex, la réduction sonochimique et le procédé sol-gel. La première étape est la synthèse d'une empreinte porogène de billes de polystyrène (latex) obtenues par polymérisation en émulsion aqueuse. La deuxième étape est la synthèse et le dépôt de NPs de métaux nobles sur la surface des billes de polymère par voie sonochimique dans l’eau. La troisième étape est la synthèse du support catalytique par un procédé sol-gel en milieu aqueux en utilisant le latex décoré et l’orthosilicate de tétraéthyle (TEOS) dans des conditions contrôlées pour moduler la porosité finale de la matrice de silice (mésoporeuse). Toutes les étapes de cette approche sont effectuées dans l'eau, ce qui limite les impacts environnementaux de la préparation du catalyseur. L'élimination du porogène (latex) par calcination génère les macropores. Le matériau résultant possède alors une morphologie inédite pour un catalyseur, avec des macropores fonctionnalisés par des NPs métalliques, dans une matrice de silice mésoporeuse. Ainsi, il a été possible de synthétiser un latex monodisperse de polystyrène (~130 nm), lequel a été décoré avec des NPs de Pt (~2.3 nm) par réduction sonochimique. Le matériau final de silice a présenté des mésopores (2-15 nm) reliant les macropores (110-400 nm) contenant les NPs de Pt. Il a été possible d'obtenir des surfaces spécifiques et des volumes poreux totaux de 615 m2/g et 0,74 cm3/g, respectivement. Dans un premier cas d'étude, des catalyseurs de Pt/SiO2 à porosité hiérarchique ont été évalués dans l'hydrogénation sélective du p-chloronitrobenzene (p-CNB) pour produire la p-chloroaniline. Ils ont présenté des activités catalytiques allant jusqu'à 91,7 ± 2,9 molCNB/(min molPt) et des sélectivités jusqu'à 100 ± 2% à 80% de conversion, par rapport à 47,7 ± 2,9 molCNB/(min molPt) et 91 ± 2%, respectivement, obtenus dans les mêmes conditions avec un catalyseur commercial. Dans un deuxième cas d'étude, des catalyseurs à base de Pd, Pd-Pt et Pd-CeO2 supportés sur de la silice à porosité hiérarchique ont été préparés et testés dans la synthèse directe du peroxyde d'hydrogène. La meilleure productivité a été obtenue avec le catalyseur bimétallique Pd-Pt avec 32500 molH2O2/(h molmétal) en batch, et la meilleure sélectivité a été obtenue avec le catalyseur Pd-CeO2/SiO2 (63 ± 2%) en semi-continu. En résumé, cette thèse propose une nouvelle méthode de préparation dans l’eau de matériaux fonctionnels à porosité hiérarchique en combinant la synthèse de latex, la réduction sonochimique et le procédé sol-gel. Il a été démontré que cette technique de préparation fournit une boîte à outils très puissante et polyvalente pour la préparation et l'optimisation des catalyseurs. Des perspectives pour améliorer davantage les morphologies et la distribution contrôlée des sites actifs sont également proposées
Roudier, Mylène. „Catalyse duale pour une synthèse énantiosélective éco-compatible“. Thesis, Aix-Marseille, 2016. http://www.theses.fr/2016AIXM4347.
Der volle Inhalt der QuelleThis manuscript is focus on the development of multicatalyzed reactions involving iminium activation and reversible neutral hydrogen transfer reaction for the synthesis of complexe enantioenriched building blocks from allyl alcohols and 1,3-dicarbonyls.An unprecedented cascade catalysis combining an iron catalyst and a pyrrolidine-base catalyst is developed for the preparation of g-fonctionalized enantioenriched alcohols in a formal redox-, atom- and step-economical approach. The efficiency of this method involving a dual catalysis and a retro-Claisen xas further demonstrated in the short synthesis of several key fragments of biologically active natural products or odorant molecule. This methodolgy was then incremented by a experimental mechanistic study allowing a better understanding of the mechanism of this transformation and leading to a new catalytic systeminvolving three different catalysts (iron complex, copper and organocatalyst). Then, we focused on the development of a new synthetic approach to enantioenriched medium-sized lactones. This methodology is based on a 1,4-Michael addition of cycloalkane-1,3-diones to a,b-insaturated aldehydes. Then, a key chemoselective reductively triggered Claisen fragmentation occurred to generate desired lactones in a rapid manner.Finally, thanks to our methodology developed during this thesis, the total synthesis of floribundane B was studied
Chenneberg, Ludwig. „Nouvelles avancées en catalyse photoredox : applications en chimie radicalaire de synthèse et en catalyse duale“. Thesis, Paris 6, 2016. http://www.theses.fr/2016PA066305/document.
Der volle Inhalt der QuelleVisible-light photoredox catalysis has emerged as a very powerful strategy to generate radical species replacing more and more tin-mediated or stoichiometric redox methodologies. The main objective of the research described in this Ph. D. thesis is to develop new synthetic methodologies in radical and organometallic chemistry, and merge them in a dual catalysis process for the preparation of elaborated molecular building blocks. In a first study, we report a photocatalytic alternative of Barton-McCombie deoxygenation based on a visible-light photoreduction of O-thiocarbamates derived from secondary and tertiary alcohols. A mechanistic investigation is presented based on fluorescence quenching and cyclic voltammetry experiments. In a second study, a challenging method of generation of unstabilized alkyl radicals by photooxidation of borate salts or hypervalent silicon species is reported. These radicals are trapped by free radical scavengers or engaged in a photoredox/nickel dual catalysis
Dandachi, Hiba. „Nouveaux Complexes Oligomères Cycliques de Salens Chiraux pour la Catalyse Asymétrique“. Thesis, Université Paris-Saclay (ComUE), 2015. http://www.theses.fr/2015SACLS106/document.
Der volle Inhalt der QuelleThis thesis work takes place in the broad context of salen chemistry. A special attention is given to corresponding chiral complexes used as versatile enantioselective catalysts for a wide range of reactions of interest. In the context of heterogeneous asymmetric catalysis, we focus specifically on the development of polymeric, cyclic, chiral salen catalysts, named calixsalen complexes. Thus, we have developed an easy access to calixsalen cobalt (III) complexes by a facile polycondensation route. These calixsalens were used as catalysts to promote the dynamic hydrolytic kinetic resolution of epibromohydrin. They are easily recovered from the reaction mixture by a simple filtration. These cyclic complexes allowed the formation of homobimetallic species responsible for an efficient dual activation of both the epoxide and water, delivering the targeted product in both high yield and selectivity.We have also reported the use of a combination of cobalt and manganese calixsalen complexes in the hydrolysis of meso epoxydes. This dual heterobimetallic system proved to be even more selective than the homobimetallic one, in which cobalt complexes were only engaged. Based on these results, we have attempted preparing heterobimetallic salen complexes, wherein two different metals should be closely associated into the same macrocycle. Towards this aim, we explored click chemistry to couple alkyne- and azide-functionalized monomeric salen complexes coordinated to two different metals
Giuseppone, Nicolas. „Les iodures de lanthanides en catalyse et catalyse asymetrique“. Paris 11, 2000. http://www.theses.fr/2000PA112122.
Der volle Inhalt der QuelleCarrée, Fabien. „Catalyse et catalyse asymétrique par les dérivés des lanthanides“. Paris 11, 2004. http://www.theses.fr/2004PA112208.
Der volle Inhalt der QuelleThis work deals with the preparation of a novel class of lanthanides iodo-binaphtoxides complexes and their evaluation as lewis acid catalysts in various organic reactions. The structure of our complexes is very interesting since they bear ionic lanthanide-oxygen bonds. Various methods have been tested to carry out the synthesis of our catalysts. Among these, two of them involve the formation of a potassium binaphtoxide as an intermediar,. The other system uses a different strategy which consists in a ligand exchange. Among these methods, the bests results have been observed by using the diphenylmethane potassium salt as base for ligands deprotonation. Catalytic activity of lanthanides iodo-binaphtoxides has then been tested in the imino-aldol reaction involving a glyoxilic imine and ketene silyl dimethyl acetal (ksa). Very high enantiomeric excesses have been observed by optimising condition reactions. Our complexes have also shown an interesting catalytic activity in primary aromatic amines meso epoxides ring-opening reactions. Lanthanum as well as samarium iodo-binaphtoxides have allowed formation of ?-amino-alcohols with up to 90% enantiomeric excesses. Moreover, use of the samarium complex has furnished a wide range of amino-alcohols, also with very good enantiomeric excesses. Finally, non-linear temperature dependant variations of enantiomeric excesses have been highlighted in our system. It has been also shown that samarium diiodide as well as samarium iodo-binaphtoxides are efficient catalysts in addition of amines on n-acyloxazolidinones or ring-opening of aziridines by aromatic amines
Motos, Blanca. „Silices fonctionnalisées contenant des espèces ioniques pour la catalyse hétérogène“. Thesis, Montpellier, Ecole nationale supérieure de chimie, 2011. http://www.theses.fr/2011ENCM0015.
Der volle Inhalt der QuelleHeterogenous catalysis is an area in continuous development due to economical, health and environmental issues. This thesis deals with the preparation of i-silica materials for the posterior application in heterogeneous catalysis. First, di-aryl imidazolium containing silica materials were synthesized by post-grafting reactions on mesoporous SBA-15. Moreover, di-alkyl imidazolium containing PMO films were prepared in presence of an anionic surfactant. Then, supported copper and palladium N-heterocyclic carbenes were synthesized from di-aryl imidazolium silica and applied to A3 reactions (Cu-NHC) and Suzuki cross-coupling reactions (Pd-NHC). Imidazolium functionalized silicas were also utilized as heterogeneous organocatalysts in Henry reactions and in reactions of cycloaddition of carbon dioxide to epoxides. Finally, PMO type materials containing amine/ammonium and zwitterionic substructures were applied to Henry and Biginelli organocatalysed reactions, respectively
Leone, Matteo. „Development of novel synthetic methodologies in photocatalysis for the preparation of (a)chiral amine derivatives“. Electronic Thesis or Diss., université Paris-Saclay, 2024. http://www.theses.fr/2024UPASF021.
Der volle Inhalt der QuelleVisible light, known for being an abundant and economical energy source, has recently become crucial in advancing sustainable catalytic chemical processes. The scientific community's substantial contributions have disclosed a broad spectrum of transformations, as outlined in the initial chapter. Among the various synthetic applications developed so far, achieving photocatalysed reactions in an asymmetric fashion remains a considerable challenge. In this specific context, our focus extends beyond the creation of new sustainable and efficient light-mediated methodologies; we are also dedicated to pioneering innovative asymmetric processes. Within this manuscript, the second chapter is dedicated to introducing a novel category of visible-light-sensitive chiral organocatalysts. These catalysts feature a covalently linked backbone of BINOL-derived Chiral Phosphoric Acids (CPAs) with various photosensitizers, such as aryl ketones and phenothiazine. Several CPAs, incorporating one or two photosensitizer moieties, were easily synthesized in a few steps from BINOL. The photophysical and electrochemical properties of these C1- and C2-symmetric chiral photocatalysts were investigated. The ketone-based chiral photocatalysts were applied in an enantioselective multicomponent tandem process, enabling the efficient synthesis of fully substituted 1,2-diamines with excellent enantioselectivities. The third chapter presents an alternative strategy for the development of asymmetric processes through photocatalysis, exploiting chiral auxiliaries. It highlights the needs of a sustainable and efficient photocatalysed methodology specifically designed for the stereoselective radical alkylation of chiral sulfinyl-imines. By utilizing readily available non-prefunctionalized radical precursors and TBADT as a photocatalyst to generate radicals through direct hydrogen atom transfer (HAT), this method has enabled the synthesis of diverse chiral amines with high yields and excellent diastereoselectivities under mild conditions. This approach proves to be effective for accessing a varied range of medically relevant compounds, encompassing both natural and synthetic α-amino acids and other α-amino compounds commonly present in approved pharmaceuticals and natural products. The fourth chapter describes a deoxygenative cross-electrophile coupling technique that combines readily available carboxylic acid-derived redox-active esters (RAEs) with aldehyde derived sulfonyl hydrazones, employing Eosin Y as an organophotocatalyst under visible light irradiation. This methodology serves as a versatile, metal-free C(sp3)−C(sp3) cross-coupling platform. Its synthetic utility as a safer and widely applicable C1 homologation of carboxylic acids was demonstrated, providing an alternative to the traditional Arndt-Eistert reaction. Furthermore, the approach allows for the direct synthesis of cyclic and acyclic β-arylethylamines using various aldehyde-derived sulfonyl hydrazones. Notably, the method is compatible with late-stage functionalization of peptides on solid-phase, simplifying the modification of intricate peptides without the need for time demanding de novo synthesis
Narbonne, Vanessa. „Catalyse par les métaux de transition : catalyse duale palladium-norbornène pour la synthèse diastéréosélective de dibenzoazépines et construction de biaryles via catalyse photorédox médiée par un complexe de ruthénium“. Thesis, Université Paris-Saclay (ComUE), 2015. http://www.theses.fr/2015SACLS115/document.
Der volle Inhalt der QuelleCatalysis by transition metal has considerably grown these decades and has become a powerful tool in organometallic chemistry. The CH ortho fonctionnalisation reaction, involving a duale palladium/norbornene catalysis, discovered at the end of the 90’s, allowed a breakthrough in the field of multi-component reactions. It provides access to polycyclic structures through an original mechanism, involving a palladacycle formation. It is the first catalytic reaction including three oxidation states of palladium (0, II and IV). In a context where the chemistry is going to be more ecocompatible, we wished taking advantage of this reaction to synthetize dibenzoazepines. They represent interesting scaffold both as organocatalysts and as bioactive compounds, however the existing synthesis don’t allow diversifying the structure of these molecules and often requiring multi-step sequences or toxic reagents. Dibenzoazepines synthesis has been realised according a three components approach from readily available reagents, a bromobenzylamine, an ortho substituted aromatic iodide and an electrowithdrawing olefin via a CH ortho fonctionnlisation/Heck/aza-Michael sequence. Remarquably, this last step presents a total diastereoselectivity. Using racemic substituted bromobenzylamine shows the same selectivity thanks to a parallel kinetic resolution-like mechanism. The access to a wide range of molecules, and the corresponding imine via a retro-Mannich mechanism using an enolisable olefin demonstrates the robustness of the ortho CH fonctionnalisation reaction. Carbon-carbon bond formation by transition metal has been largely developped since decades. However, it often generate waste and use toxic reagent at high temperature. Photoredox catalysis is a great success recently and have the advantage to use light as energy source and small amounts of metal and organocatalyst. We have developed a method of biarylic coupling via a photoredox catalysis mediated by a ruthenium complex. Arene diazonium, the precursor coupled, have the advantage to generate diazote as waste, and realise an homolytic aromatic substitution on aromatic and heteroaromatic acceptors. Moreover, it takes place at room temperature without base. It is an alternative for the biarylic coupling and an green chemistry
Bilel, Hallouma. „Catalyse et métathèse : valorisation de produits naturels par catalyse organométallique“. Thesis, Rennes 1, 2015. http://www.theses.fr/2015REN1S030/document.
Der volle Inhalt der QuelleThe utilization of renewable feedstocks arising from biomass has recently found a renewed interest for economic and ecological reasons. Triglycerides arising from oil seeds, terpenes extracted from plants, and phenolic derivatives found in lignin represent important families of natural molecules with important potential for the access to high added value products. In this context, homogeneous catalytic transformations offer interesting perspectives towards green and sustainable chemistry. Olefin metathesis in the presence of commercially available ruthenium catalysts has given access to new functionalized terpenes using cross metathesis with electron deficient alkenes. The same type of reaction applied to eugenol derivatives controlling at the same time the position of their terminal double bond has provided access to new allylic derivatives of phenol by using acrylates, acrylonitrile and acrylamides as cross metathesis partners. Finally a cascade reaction involving cross metathesis of fatty ester, terpene and eugenol derivatives with allylic chlorides followed by an elimination reaction has led to a general method for the synthesis of terminal conjugated dienes. These sequential reactions in one pot allow decreasing the amount of wastes, which are usually generated during intermediate treatments. The reported catalytic transformations of renewable resources have been carried out in green solvents such as dialkyl carbonates or without solvent under neat conditions, and thus fulfill several criteria of green chemistry
Han, Xu. „Development of innovative methodologies in phosphine organocatalysis and enantioselective gold(I)-catalysis“. Thesis, Université Paris-Saclay (ComUE), 2019. http://www.theses.fr/2019SACLS568.
Der volle Inhalt der QuellePhosphines play a major role in modern organic chemistry. In the field of catalysis, organophosphorus derivatives can be applied as catalysts in numerous transformations by itself, as organocatalysts, or as ligands in organometallic catalysis. This thesis focused on the application of phosphines both in phosphine organocatalysis and in asymmetric gold(I) catalysis. In the organophosphorus catalysis part, we have developed a phosphine-catalyzed Michael addition/Wittig reaction by using a well-chosen cyclic phosphine catalyst. In this process, silane was used as reducing agent to selectively reduce in situ the phosphine oxide. A series of highly functionalized 1,2-dihydroquinolines were prepared. Besides, a new olefination process was discovered for the synthesis of succinate derivatives. Detailed mechanism research was carried out with H/D exchange experiments. In the asymmetric gold(I) catalysis part, we have developed two new methodologies based on cyclization reactions of 1,n-enyne substrates. A 1,5-enyne cyclization/nucleophilic addition reaction was first developed with an acyclic TADDOL-derived phosphoramidite-Au(I) complex. Twenty examples were carried out with good to excellent yields and up to 94% enantiomeric excess. For the 1,6-enyne cyclization/intramolecular nucleophilic addition sequence, we have synthesized a range of racemic tetracyclic and pentacyclic compounds in high yields. The enantioselective version of this transformation was carried out successfully with both high reactivity and enantioselectivity
Bouquin, Maxime. „Formation de liaisons C-C et C-hétéroatome catalysée par des métaux plus respectueux de l'environnement ou en leur absence“. Electronic Thesis or Diss., Montpellier, Ecole nationale supérieure de chimie, 2022. https://theses.enscm.fr/ENSCM_2022_BOUQUIN.pdf.
Der volle Inhalt der QuelleThe proposed research program is within the general framework of green syntheses for sustainable chemistry through the development of new catalytic systems performing challenging reactions. More specifically, the objectives of our project lie within the framework of transition metal catalyzed or transition metal free mediated/catalyzed arylation of nucleophiles (coupling of N-, O-, S-, P-, C-nucleophiles with aromatic halides). This type of reaction, which allows the formation of C-N, C-O, C-C, C-S or C-P bonds, is without any doubt one of the most important transformation in organic synthesis. Numerous types of catalytic systems have been described in this field, mainly based on nickel, palladium and more recently copper. The families of aromatic molecules obtained (Ar-Nu) by these reactions are very interesting building blocks since they constitute the main part (about 70%) of active molecules in life sciences (pharmaceuticals, agrochemicals) and of many material precursors. This reaction is thus of major importance for industry. The proposed research program, which focuses on the discovery of novel competitive and environmentally friendly catalytic systems for this type of reactions, belongs to the field of sustainable development (non-toxic, non-polluting, low cost catalytic systems – REACH regulation). The project will be implemented following 2 synthetic objectives (Transition metal free mediated C-C and C-heteroatom bond formations and New concept for the Cu-catalyzed arylation of nucleophiles from ArCl), complemented by a transversal one (Mechanistic study)
Donck, Simon. „Catalyse supportée sur nanotubes de carbone“. Thesis, Université Paris-Saclay (ComUE), 2015. http://www.theses.fr/2015SACLS042/document.
Der volle Inhalt der QuelleThis PhD thesis deals with the catalysis supported on carbon nanotubes. Several aspects have been studied such as electrocatalysis for hydrogen production form water, catalysis for organic synthesis and electrocatalysis of the oxygen reduction reaction. Many different catalysts have been synthesized based on supramolecular assembly of amphiphilic molecules around carbon nanotubes or assembly of polyaromatic molecules at the surface of the nanotubes. These catalysts are made of metallic complexes or metallic nanoparticles. These catalysts have been successfully used to perform the reactions mentioned above
Kieffer, Raphaëlle. „Développement de nouveaux catalyseurs pour la dépolymérisation de la lignine par voie d’oxydation“. Thesis, Lyon 1, 2015. http://www.theses.fr/2015LYO10124/document.
Der volle Inhalt der QuelleLignin is one of the most abundant biopolymers on earth. It is issued from plants and represents the largest source of aromatics in biomass. Projects aiming at depolymerizing lignin to obtain value-added small molecules for the chemical industry are more and more developed due to the high potential of this bio-resource. The goal of our project was to develop a new catalytic system for the depolymerization of lignin. We have been interested in designing new homogeneous and heterogeneous catalysts based on the known structure of the Fe(TAML) complex. We have studied their reactivity and stability under oxidative catalysis conditions, and have compared them to the characteristics of the existing Fe(TAML). To do so, the catalysis study has been realized on lignin small model molecules to avoid the analytical problems related to a polymer backbone. In a first hand, we will present the strategy of functionalization of the known TAML ligand to design new complexes to be grafted on a silica support. In a second hand, we will talk about the results of oxidative catalysis in homogeneous and heterogeneous conditions, and the influence of the ligand structure change on the activity of the catalysts
Lagasse, Franz. „Evaluation de catalyseurs racémiques : analyse du problème, présentation d'une approche possible“. Paris 11, 2002. http://www.theses.fr/2002PA112106.
Der volle Inhalt der QuelleA new direct method for evaluating the efficacy of a chiral catalyst from his racemic mixture has been proposed and developed. The same enantiomer of a catalyst should be involved two times in the double sequential transformation of a bifonctionnal substrate. A mathematical study has shown that the enantioselectivity of the first step is connected to stereoselectivities of the reaction by simple equations. Their validities were confirmed by measured and calculated stereos- electivities with racemic and chiral catalysts. The diastereoselectivity was proposed as an indicator of the enantioselectivity of the catalyzed reaction by an enantiopur catalyst, if no substrate control occured. A diketone borane reduction was studied with both chiral and racemic catalysts. Strong diastereoselectivities were obtained (80 % de) with racemic catalysts certainly due to a double sequential reduction of the diketone by the same enantiomer of the racemic catalyst. The calculated enantioselectivities from the diastereoselectivities are in good agreement with those mesured in a monoketone reduction. Some assays were performed with racemic catalysts applied to other catalytic reactions (hydrosilylation and hydrogen transfer reduction of diketone). No diastereoselectivities were observed. It is suggested that the second step is randomly catalyzed by one or the other enantiomer of the racemic catalyst. A mechanism for borane diketone reduction catalyzed by oxazaborolidine was proposed. Future prospects were discussed to solve and to limite the problem of catalyst diffusion and to oblige each enantiomer of a racemic catalyst to sequentially react with the two prochiral sites of the same substrate molecule
Nguyen, Hoang-Anh. „La catalyse homogène“. Paris 5, 1988. http://www.theses.fr/1988PA05P186.
Der volle Inhalt der QuelleDumeignil, Franck Payen Edmond Grimblot Jean. „Catalyse et environnement“. Villeneuve d'Ascq : Université des sciences et technologies de Lille, 2007. https://iris.univ-lille1.fr/dspace/handle/1908/177.
Der volle Inhalt der QuelleSynthèse des travaux en français et curriculum vitae. Recueil de publications en anglais non reproduit dans la version électronique. N° d'ordre (Lille 1) : 501. Titre provenant de la page de titre du document numérisé. Bibliogr. 5 p. Liste des publications et des communications.
Le, Callonnec Francois. „Nouveaux développements dans la chimie des sels de diazonium en catalyse organométallique : catalyse hétérogène en milieux aqueux“. Thesis, Bordeaux, 2014. http://www.theses.fr/2014BORD0044/document.
Der volle Inhalt der QuelleDiazonium salts are reactive and versatile when used as electrophiles. Unfortunately, their reputation as instable compounds strongly limited their use in chemical synthesis. This work lead to the discovery of new procedure for a safer and more environmentally friendly use of diazonium salts in organometallic coupling reactions. We studied palladium catalised carbon-carbon coupling reactions and copper catalyzed C-H arylatons. A major part of this work is also focalized in the development of new heterogeneous catalysts. New catalysts for the Meerwein reaction were also discovered. Finally, the last part of this research work focused on new active heterogeneous supports as nanoreactors for organometallic reactions
Bourouina, Amine. „Desperately Seeking For The Catalytic Species In Suzuki-Miyaura Reaction“. Thesis, Lyon, 2019. http://www.theses.fr/2019LYSE1258.
Der volle Inhalt der QuelleThe use of ligand-free supported Pd is an attractive idea because it avoids problems related to the presence of the ligands (cost and toxicity). Also the catalyst is easily recovered at the end of the reaction by conventional methods such as filtration or decantation. Thus, it is easier to meet regulations in Active Pharmaceutical Ingredients (<10 ppm). However, the presence of molecular or atomic Pd species in solution when using solid catalysts has created an important discussion on the true nature of catalysis. This last could be heterogeneous on the surface of the supported Pd or homogeneous via species in solution. In this work the Suzuki-Miyaura (SM) reaction was chosen as the target reaction. In the absence of an overall kinetic study in the literature, a kinetic study was carried out with a molecular catalyst. It provided a mechanistic law that represents the homogeneous part of the reaction. Furthermore, an innovative test (“split flow reactor”) has been proposed. It permits to distinguish between the homogeneous and heterogeneous contributions and to determine the nature of the species that catalyze the reaction. It was used in the reaction of different iodo, bromo, and chloro aryls. Several supported catalysts were used by varying the nature of the support and the oxidation state of Pd (Pd (0) and Pd (II)) in the initial precursor. Finally, a reactor model has shown that for the same iodoaryl, whatever the nature of the solid, the supported Pd seems to release the same active species in solution. These species catalyze the SM reaction with initial activities of the order of 500 000 h-1. The split flow reactor is a new, easy-to-use test. Accompanied with online analysis techniques, it can be used to track the evolution of catalytic species in real time and to study other chemical systems
Languet, Morgan. „Fonctionnalisation d'hétérocycles par catalyse organométallique et photorédox“. Thesis, Paris 6, 2017. http://www.theses.fr/2017PA066497/document.
Der volle Inhalt der QuelleThe work presented in this manuscript concerns two methods of functionalization of heterocycles by using organometallic catalysis. Firstly, the introduction of an olefinic moiety at the C3 position of 5-membered heterocycles was achieved by a catalytic system based on the use of a rhodium(III) salt and a silver salt. Despite some limitations in the scope, this method was found to be particularly effective for the introduction of an acrylate group at the C3 position of these heterocycles. Furthermore, the use of carbamate as a directing group, has allowed a large number of post-functionalization reactions such as cross-couplings catalyzed by nickel and iron salts. The second part of our work was devoted to the arylation of 2-quinolone at the C3 position by photoredox catalysis. More particularly, under mild conditions (ambient temperature, without additives), the arylation of these 2-quinolones was carried out using aryldiazonium tetrafluoroborate salts as a precursor of aryl radicals. Control experiments, measurements of UV-visible absorption spectra and an ON/OFF experiment were also performed to elucidate the mechanism of this photocatalysed arylation
Magné, Valentin. „Synthèse d'hétérocycles chiraux par catalyse à l'Au(I) et développement de nouveaux phosphahélicènes pour la catalyse énantiosélective“. Thesis, Université Paris-Saclay (ComUE), 2017. http://www.theses.fr/2017SACLS386/document.
Der volle Inhalt der QuelleAu(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
Karnat, Alexandre. „Nitrogen- and selenium-containing heterocycles, synthesis, reactivity and application as glutathione peroxidases mimics“. Electronic Thesis or Diss., Bordeaux, 2024. http://www.theses.fr/2024BORD0037.
Der volle Inhalt der QuelleNumerous selenazacycles have attracted attention because they can mimic natural selenoenzymes (Glutathione Peroxidase, GPx), dedicated to the reduction of hydroperoxides. These mimics are catalytical antioxidants with a few envisaged as anti-inflammatory active ingredients. Currently, no pharmacological option based on a GPx mimic is available, but chemical hybridization of these motifs showed promising preliminary results. Besides, the chemical reactivity of these heterocycles is rarely explored, especially as organic selenium sources for the synthesis of selenated scaffolds. During this PhD, we took interest in two selenium- and nitrogen-containing rings, 1,2-benzisoselenazole and 1,2-benzisoselenazine, and explored both their reactivity and potential as GPx mimics. We developed new cleavage methodologies of the Se-N bond of Ar-Se-N-C moieties in basic conditions. This strategy allowed the synthesis of arylselenides through a postulated in situ formation of phenylselenolate anions. Both studied cores could be employed as stable precursors. We then developed a synthetic platform based on a known GPx mimic (BXT-51072) possessing a 1,2-benzisoselenazine ring, toward the synthesis of conjugates. A derivative exhibiting an azide motif was synthesized to hybridize the scaffoldvia CuAAC reactions. Furthermore, arylselenenyl halides potentially exhibiting GPx-like activities could be obtained through the addition of alkyl halides to 1,2-bensizoselenazoles
Shcheholeva, Iryna. „Synthèse orientée vers la diversité pour l'inhibition de microARN oncogènes“. Electronic Thesis or Diss., Université Côte d'Azur, 2024. https://intranet-theses.unice.fr/2024COAZ5006.
Der volle Inhalt der QuelleConstituting a major part of the transcriptional output and given their function in modulation of epigenetics, noncoding RNAs (ncRNAs) carry an important role in disease development, but remain under-exploited biological targets. MicroRNAs (miRs) are 19 - 25 nucleotide long single-stranded RNAs and represent a major ncRNA family that is primarily known for their role in the control of gene expression. Each microRNA indeed inhibits translation of multiple messenger RNAs, and dysregulation of microRNAs is critical to pathogenesis and oncogenesis in particular. Specifically, microRNA-21 has been in the spotlight after its consistent overexpression in cancers as reported in a study that profiled 540 clinical samples from cancer patients. Thus, inhibition of miR-21 function holds the promise for both an efficient therapy alone and as an adjuvant to the existing treatments.The goal of this PhD work was to develop a small-molecule inhibitor of this oncogenic microRNA, tackling the last step of its biogenesis, an enzymatic cleavage by Dicer. We focused on the latter to mitigate a challenge associated with ssRNA as a biological target, such as the undefined secondary structure. In this thesis, the precursor of miR-21, a longer and structured preceding transcript, was used as a target and small-molecule ligands were designed to bind to its structured regions and impede its recognition via Dicer. The library of the drug-like RNA-focused ligands was designed de novo and synthesised using efficient catalytic methodologies and their activity was assessed in vitro using fluorescence-based biochemical assays with human recombinant Dicer. The study revealed several novel small molecule binders and inhibitors of oncogenic microRNA-21 in the low micromolar range. The binding mechanism of the best compounds was studied with biophysical and in silico methods to establish structure-activity relationships and improve the observed activity. This thesis discloses new promising scaffolds that inhibit miR-21 maturation of miR-21 in vitro and provide a blueprint for targeting this noncoding RNA with small molecules
Gobé, Valérian. „Cyclisations métallo-catalysées pour la synthèse de composés indoliques polycycliques“. Thesis, Université Paris-Saclay (ComUE), 2015. http://www.theses.fr/2015SACLS057/document.
Der volle Inhalt der QuelleThe indole ring is one of the most prominent heterocycle in natural products or bioactive compounds. The access to complex structures featuring several cycles, stereogenic centers, is one of the main challenge en route to the discovery of new potentially bioactive structures. During this PhD work, we developed metallo-catalyzed cyclizations of tetrahydro-β-carbolines presenting an unsaturated function to access to complex chiral, polycyclic compounds. The asymmetric organocatalyzed Pictet-Spengler reaction was used as a key step for the control of the asymmetry, starting from N-allyl tryptamines and allenaldehydes. The corresponding tetrahydro-β-carbolines were obtained in excellent yields and enantiomeric excesses.Several cyclization reactions were developed using these substrates, catalyzed by Pd(0) or Au(I) complexes, furnishing the targeted chiral tetracyclic derivatives. The mechanisms of these reactions, the regio-, chem- and diastereoselectivity of these reactions was studied. The large numbers of compounds that have been obtained via these routes present a large structural diversity that will hopefully lead to important findings in the field of bioactivity determination
Poupart, Romain. „Nanoparticules métalliques@polymères poreux : matériaux hybrides innovants pour la catalyse supportée“. Thesis, Paris Est, 2017. http://www.theses.fr/2017PESC1174/document.
Der volle Inhalt der QuellePorous materials based on polymers have been the subject of intense and various researches since their discovery until now. Their unique and remarkable properties, like their easy functionalization or their large porosity range reachable for instance, coupled with their low production cost makes them attractive for numerous applications. Among them, supported catalysis is booming, especially since the rising of nanoparticles. During this Ph.D. contribution, we have developed different polymeric materials, which could be used as support, focusing mainly onto three types: bulky materials, porous polymeric matrixes into capillaries and porous polystyrene arising from the selective degradation of diblocks copolymers.Firstly, different strategies have been employed for the immobilization and the generation of nanoparticles onto bulk materials. On the one hand, the synthesis of a monomer, bearing a disulphide bridge which can, after a reduction step, free a thiol moiety allowing us to anchor gold nanoparticles. On the other hand, a new route to reduce nanoparticle has been employed using gaseous hydrogen. In another part, the syntheses of different polymeric matrixes into capillaries have been made. First, we used an already known matrix, based on N-acryloxysuccinimide -after modification step via thiol-ene reaction and nucleophilic substitution by amines- to anchor copper or gold nanoparticles, respectively. Also, a new matrix based on cyclic carbonates has been used, after modification, to immobilized platinum nanoparticles. Finally, starting from diblocks copolymers possessing different junctions between both blocks (disulphide bridge or acetal), porous polystyrenes have been obtained. The copolymers bearing an acetal have been implemented to immobilized gold nanoparticles, catalysing several reactions like nitro reduction, boronic homocoupling as well as the cascade reaction of both
Dandach, Amar. „Transformation de la cellulose en bioproduits : une approche intégrée couplant la catalyse enzymatique et la catalyse hétérogène“. Thesis, Lyon, 2018. http://www.theses.fr/2018LYSE1129.
Der volle Inhalt der QuelleThis thesis deals with the possibility of combining heterogeneous catalysis and enzymatic catalysis in a cascade reaction for cellulose transformation into value-added products. The enzymatic pretreatment was chosen as the first cellulose transformation step to weaken the cellulose structure which is carried out in a buffer solution of acetic acid and sodium acetate at a pH 4.75, at 50°C. This step is selective, producing mainly glucose, and it has structurally modified the residual cellulose by only decreasing its degree of polymerization (DP) by providing new reducing ends without affecting its crystallinity. The challenges of the second step, heterogeneous catalysis, which is done in a closed autoclave at a temperature greater than or equal to 190°C, were then to find a heterogeneous catalyst that can tolerate the buffered enzyme reaction medium, that can have a favored activity on lower DP celluloses and that can valorize the obtained glucose and cellulose in identical conditions. Among the different families of catalysts tested, the metallic catalyst based on Pt/carbon was shown to be more efficient than the other Lewis and Brønsted acid catalysts due to its resistance to the buffer medium and its abilities to valorize glucose and cellulose in equivalent conditions despite the independence of this type of catalyst to the reduction of the DP of the pretreated cellulose. It allowed to selectively convert cellulose into propylene and ethylene glycols at 240°C in a cascade reaction including an enzymatic catalytic step and a heterogeneously catalyzed one
Bueno, Alejandra. „Catalyst supports with hierarchical and radial porosity : preparation, characterization and catalytic evaluation“. Thesis, Lyon, 2019. http://www.theses.fr/2019LYSE1249.
Der volle Inhalt der QuelleThe vast majority of chemical processes are catalytic. Within the heterogeneous catalysis, industrial catalysts are bodies whose size ranges between 1 mm to 1 cm. For most catalysts, the active phase (i.e. metal nanoparticles) is dispersed in a mesoporous support having a high specific surface area. To overcome the problem of internal diffusional limitation, a secondary network of macropores is introduced within the catalyst support. This improves the diffusion of substrates. However, in the case where the catalytic reaction is particularly fast, the diffusion inside the porous support can remain limiting (Thiele modulus), resulting in a loss of catalytic effectiveness. The objective of this thesis is to study the catalytic effectiveness of a new alumina-based support shaped into spherical pellets, owing a radial macroporosity. In order to quantify the impact of this new porous structure, two model catalytic reactions were chosen to test the catalysts: CO oxidation and isooctane cracking. The catalytic activity was compared to reference commercial supports owing hierarchical porosity. For both reactions, the new support with radial porosity increases the activity from 25 to 95% approximately. On the basis of a fine characterization of the porosity of the beads (adsorption N2-77k, porosimetry Hg, X-ray microtomography), the catalytic activities were modeled. We conclude that the impact on the catalytic activity is essentially due to the radial porous design
Bareille, Laurianne. „Dérivés du titane en catalyse : nouvelles réactions de couplage et catalyse bimétallique“. Dijon, 2005. http://www.theses.fr/2005DIJOS040.
Der volle Inhalt der QuelleThe allyltitanation reaction was widely studied in our laboratory but always with a stoichiometric amount of titanium. In order to perform this reaction in a catalytic way, we used a stoichiometric amount of a cheap silane, PMHS, and titanocene difluoride. After optimization, the system Cp2TiCl2/isoprene/BuLi/PMHS gave the bests results. Then we realised the fisrt trans-1,4 hydrosilylation of dienes catalyzed by an "early" metal. This reaction was extended to many dienes and silanes and we proposed two catalytic cycles. These allylsilanes have been involved in Hosomi-Sakurai reactions. Finally, we prepared new bimetallic complexes TiF2-Ru, Ti(O2CPh)2-Ru and Ti(binaphtol)-Ru that are able to catalyse some reactions ; we can now imagine their implication in "cascade reactions" which would use the two metallic centers
Wang, Xia. „Artificial Photosynthesis : Carbon dioxide photoreduction and catalyst heterogenization within solid materials“. Thesis, Paris Sciences et Lettres (ComUE), 2017. http://www.theses.fr/2017PSLET025/document.
Der volle Inhalt der QuelleIn the context of global warming and the necessary substitution of renewable energies (solar and wind energy) for fossil fuels, efficient energy-storage technologies need to be urgently developed. Recently, energy storage via the reduction of CO2 has seen renewed interest. Although reduction of CO2 into energy-dense liquid or gaseous fuels is a fascinating fundamental issue, its practical implementation in technological devices is highly challenging due to the high stability of CO2 and thus the endergonic nature of its transformation. Furthermore, the reactions involve multiple electrons and protons and thus require efficient catalysts to mediate these transformations.The objective of this thesis is to investigate different strategies for the storage of solar energy in chemical compounds, through visible-light-driven CO2 reduction. This thesis comprises of two main parts. After an introduction, the first part describes the investigation of homogeneous catalysts in combination with a photosensitizer, either separately or connected covalently. Due to the easily-tunable synthesis and facile characterization of molecular catalysts, homogeneous photosystems are more controllable and can give deep insight into product selectivity and mechanistic issues.With regards to future applicability, however, homogeneous catalysis often suffers from additional costs associated with solvents, product isolation and catalyst recovery, amongst other factors. The integration of molecular catalysts into solid platforms offers the possibility to maintain the advantageous properties of homogeneous catalysts while moving towards practical system designs afforded by heterogeneous catalysis. The second part of this thesis is therefore the immobilization of molecular catalysts within solid materials, namely MOFs and PMO. The ultimate goal of this thesis is to incorporate both catalyst and photosensitizer into the solid support
Santori, Pietro Giovanni. „Investigation of electrocatalysts for anion-exchange membrane fuel cells“. Thesis, Montpellier, 2019. http://www.theses.fr/2019MONTS129.
Der volle Inhalt der QuelleThis PhD thesis investigates the synthesis, structural characterization and oxygen reduction reaction (ORR) activity of Fe-N-C catalysts and composites of Fe-N-C and manganese oxides, and their application at the cathode of anion exchange membrane fuel cells (AEMFCs). Compared to proton exchange membrane fuel cells (PEMFCs), where platinum is today needed to reach high performance, AEMFCs hold the promise to reach high performance without precious metals in their catalysts. While Fe-N-C catalysts are currently investigated as an alternative to Pt/C for PEMFC cathodes, they suffer from lower activity and lower durability in the acidic medium of PEMFCs. In contrast, both the ORR activity and stability of Fe-N-C catalysts can be expected to be significantly improved in AEMFC.This PhD work demonstrates the high activity, stability and durability in alkaline medium of Fe-N-C catalysts with atomically-dispersed FeNx sites. They were prepared from a mix of ZIF-8 and iron salt, pyrolyzed in argon (Fe0.5-Ar) and then ammonia (Fe0.5-NH3). The activity was measured in a rotating disk electrode (RDE) and in AEMFC, while the stability was measured in RDE and in operando with mass spectroscopy (ICP-MS) coupled with a scanning flow cell, in both acid and alkaline media. The latter setup was used to measure Fe dissolution in operando. It was evidenced that, in oxygenated acid electrolyte, the iron leaching rate of the most active Fe-N-C catalyst (Fe0.5-NH3) is 10 times faster compared to the less active Fe0.5-Ar. This explains the reduced stability of ammonia-treated Fe-N-C catalysts in operating PEMFC. In contrast, in alkaline medium, very little demetallation was observed even for Fe0.5-NH3. This was correlated with almost unchanged activity after load cycling in RDE. The nature of the active sites was investigated with X-ray absorption spectroscopy, including in operando measurements.Then, to minimize the amount of peroxide species during ORR on Fe-N-C, different manganese oxides were synthesized and their activity for ORR and hydrogen peroxide reduction reaction (HPRR) were evaluated, while operando manganese dissolution was investigated with ICP-MS. It was found that even the most stable Mn-oxide, Mn2O3, leached a significant amount of Mn during ORR in alkaline medium. It was further demonstrated that the Mn leaching is associated with hydrogen peroxide produced during ORR. Composites of Fe0.5-NH3 and Mn-oxides were then investigated for ORR and HPRR. Improved selectivity during ORR was observed for all composites relative to Fe0.5-NH3 alone, but the effect was strongest for Mn2O3.Before investigating such catalysts in AEMFC, a study on the compatibility between different ORR and/or hydrogen oxidation reaction catalysts (Pt/C, Fe0.5-NH3, PtRu/C, Pd-CeO2/C) and anion exchange ionomers was performed in RDE in 0.1 M KOH. The study identified issues between the investigated ionomers and catalysts having low metal contents on the carbon support (Fe0.5-NH3, Pd-CeO2/C).The catalyst Fe0.5-NH3 and its composite with Mn2O3 were then investigated in AEMFC with an ethylene-tetrafluoroethylene ionomer. Both cathode catalysts reached a current density of ca 80 mA cm-2 at 0.9 V, with relatively low loading of 1.0-1.5 mg catalyst·cm-2. The peak power density with H2/O2 reached 1 W cm-2 at 60°C with a low density polyethylene AEM and 1.4 W cm-2 with high density polyethylene AEM at 65°C. By comparison, a current density of ca 70 mA cm-2 at 0.9 V and peak power density of 1.5 W cm-2 was reached with 0.45 mgPt cm-2 at the cathode (40 wt% Pt/C) with low density polyethylene AEM at 60°C. A durability test of 100 h at 0.6 A cm-2 in air showed good stability of the Fe0.5-NH3 catalyst.In conclusion, this work highlights the promising application of Fe-N-C catalysts at the cathode of AEMFCs for replacing precious metal catalysts
Darcos, Vincent. „Photodimérisation par catalyse supramoléculaire“. Bordeaux 1, 2000. http://www.theses.fr/2000BOR10563.
Der volle Inhalt der QuelleThis work describes the use of hydrogen bonding to direct photoinduced dimerisation reactions of styrenes, cinnamate esters and stilbenes possessing diaminotriazine substituents. The dimerisation proceeds slowly in dilute (0,01 M) dichloromethane solution to give a mixture of photodimers. In the presence of a suitable template molecule, acting as a supramolecular catalyst, the formation of some of the photodimers is enhanced. It is shown that the observed rate acceleration is due to the formation of hydrogen-bonded trimeric species in which the photoactive double bonds are held in close proximity, and that dimerisation occurs topochemically within the supramolecular architecture
Attoui, Mariam. „Nanocatalyseurs hélicoïdaux chiraux à base de polyoxométallates pour les réactions d’oxydation énantiosélectives“. Thesis, Bordeaux, 2018. http://www.theses.fr/2018BORD0447/document.
Der volle Inhalt der QuelleChiral polyoxometalates (POMs)-based materials have attracted particular attention in recent years due to their remarkable properties and potential application, especially in the field of catalysis. The goal of this thesis is to design a series of enantiopure nanohelical structures based on polyoxometalates (NANOPOM), for their use as heterogeneous oxidation catalysts. Two approaches were used to prepare these new materials. The first one based on the immobilization of POMs on silica nanohelices and nanoribbons by electrostatic and direct adsorption grafting. These inorganic structures increase the stability and make them less sensitive to external environment. The second approach is to include POM units within the structure of organic nanoribbons and nanohelices during self-assembly of 16-2-16 (L)- or (D)-tartrate gemini amphiphile and POM in water. The characterization of these NANOPOM hybrids by using various techniques such as 31P NMR, UV-Vis, DRIFT, Raman, TEM, HR-TEM and EDX was performed and confirms the structure of these materials, especially the grafting of POM to helical supports. These materials are generally stable, and the induction chirality to the POM anion was confirmed by circular dichroism, highlighting the enantiopurity of these NANOPOM materials. The catalytic properties of these POM hybrids have been tested in the oxidation of sulfides. They are active and recoverable catalysts, unfortunately with no significant enantioselectivity observed in the condition used. We expect that new NANOPOM systems in which POM units are introduced within the structure of nanostructure during gel formation, followed by silica transcription will be more stable, an important feature for their use as recoverable catalyst
Sachse, Alexander. „Synthèses de microréacteurs à base de monolithes siliciques et zéolithiques à porosité hiérarchique pour le développement de la catalyse en flux“. Thesis, Montpellier, Ecole nationale supérieure de chimie, 2011. http://www.theses.fr/2011ENCM0006/document.
Der volle Inhalt der QuelleThe aim of this work is the synthesis and the functionalization of silica monoliths with hierarchical porosity and their use as catalytic microreactors for flow-through chemistry. A reproducible synthesis of the silica monoliths was elaborated. The functionalization with a variety of functions has been performed, such as aminopropyl groups, aluminium oxide, MOFs (CuBTC), and palladium nanoparticles. These functionalized silica monoliths have been used for the Knoevenagel condensation, Diels-Alder reaction and Fiedländer reaction, where they show increasing productivities compared to classically used reactors (batch, packed-bed) and enable process automation. The pseudomorphic transformation of silica monoliths in zeolite monoliths in the SOD and LTA phase has been elaborated. We have preformed the first implementation of a macroporous zeolite monolith as microreactor for the fine chemical production in flow continuous conditions. The zeolite monoliths have been tested for dynamic ion exchange and are promising materials for the use as decontaminants of radioactive discharges
Michalska, Malina. „Development of new gold-catalyzed strategies in N-acyliminium ion chemistry“. Thesis, Le Havre, 2013. http://www.theses.fr/2013LEHA0027/document.
Der volle Inhalt der QuelleThe research project is centred on the development of new gold catalyzed transformations in N-acyliminium ion chemistry. The objective of our first part of the project is to develop an enantioselective gold-catalyzed 5 exo-dig intramolecular hydroalkoxylation/aza-Ferrier-Petasis rearrangement sequence. This sequence could give an asymmetric and atom economic expeditious access to the structure of hydropyrrolizidines, which are known to be potential biologically active compounds. A second part of the project is devoted to the development of the first catalytic alkynylation of cyclic N-acyliminium ions using N,O-acetals. This type of reaction is potentially an important transformation, giving rise to propargylic amine derivatives amenable to further interesting synthetic manipulations en route to nitrogen-containing natural products and some analogs. Considering our objectives, key features is the use of TMS alkynes in conjunction with gold complexes that have been paired with poorly nucleophilic counter-ions. To broaden the scope of catalysis based on gold, it is important to extend the range of substrates and functional groups that can be activated by gold complexes. A final section is devoted to the sequential catalysis which designs the promotion of catalytic multistep processes. In this way, two fundamentally distinct chemical transformations are catalytically promoted in a single flask. This research area allows the rapid and efficient reach of complex molecular frameworks with improved yields and resource efficiency. Therefore, this is an exciting theme in modern organic synthesis that has recently stimulated the report of numerous excellent contributions
Deraedt, Christophe. „Nanoréacteurs pour la catalyse en milieux aqueux“. Thesis, Bordeaux, 2014. http://www.theses.fr/2014BORD0430/document.
Der volle Inhalt der QuelleThis thesis concerns the synthesis by “click” CuAAC reactions of newnanomaterials that have various applications, in particular in catalysis. Thesemacromolecules are dendrimers, supported dendrimers and polymers that contain1,2,3-triazole rings and were used in the stabilization of essentially palladiumnanoparticles (PdNPs). These PdNPs are extremely active in the catalysis in greensolvents of C-C coupling, reduction of 4-nitrophenol and selective oxidation ofalcohols. The use of these nanoparticle catalysts at the ppm level shows theirefficiency and their ecological aspect. The integration of biferrocene units in thepolymers allowed expanding their applications to electrochemical sensors, reductantsof metallic ions to nanoparticles, polyelectrolytes, polyelectrochromic, and mixedvalentcomplexes. The impregnation of PdNPs stabilized by dendrimers on magneticsupport led to the increase of the catalyst robustness and recyclability using amagnet
Boscaro, Paolo. „One-pot synthesis of structurated of TiO2 materials easy to handle (not nanoparticles) for photocatalysis under visible light and sunlight“. Thesis, Montpellier, Ecole nationale supérieure de chimie, 2016. http://www.theses.fr/2016ENCM0009.
Der volle Inhalt der QuelleThe aim of this study is to develop titania based materials able to perform photocatalytic reaction in flow condition, under sunlight or visible light, with special physical and chemical properties in order to overcome common photocatalysts’ deficiencies like: mechanical stability, pressure drop, low mass transfer and contact time, reduced wavelength range absorption, photo-generated charge lifetime, and in general all features that limit photocatalysts efficiencies. Three synthesis methods have been developed and optimized to obtain TiO2 monoliths with shape and dimension that can be adapted to any specific application. TiO2 monoliths, displaying bimodal macro-mesoporous interconnected network together with an elevated mechanical and chemical stability, have been used as flow photocatalyst microreactor under different flow rate conditions. Synthesized monoliths displayed enhanced visible light absorption, enabling them to efficiently operate in a vast range of illumination. TiO2 monoliths absorption on the visible range of the spectrum is attributed to carbon-nitrogen containing species within the material. Orange G degradation in aqueous medium have been performed both in batch and flow reactors under sunlight, visible light and UV light. All reactions resulted in complete mineralization of pollutant, with higher degradation rate than TiO2 nanoparticles benchmark material (P-25) when visible light is used. No photocatalyst deactivation have been detected after 85 hours of wastewater treatment in flow conditions. Similar TiO2 material, with a free-standing thick-film shape, have been used to perform photocatalytic water splitting under visible light. Another strategy has been developed to synthesize a TiO2/CuO self-standing film to enhance charge separation giving unexpected results in terms of hydrogen production
Zhao, Guangkuan. „Reduction of thioketals by TMSCl/NaI association and synthesis of heterocycles from ortho-substituted arylalkynes“. Thesis, Université Paris-Saclay (ComUE), 2019. http://www.theses.fr/2019SACLS392.
Der volle Inhalt der QuelleThis thesis is divided into two distinct parts. The first show that, after a comprehensive study of thioketals desulfurization reactions listed in the literature, the use of TMSCl / NaI combination is a modern method of choice to reduce thioketals since it does not require any toxic metal. In a second part, we have been interested in the synthesis of heterocycles (isocoumarins, benzothiophenes and indoles) by the study of original heterocyclization reactions. The thesis is presented with the presentation and discussion of publications (7)
Savourey, Solene. „Nouveaux procédés de réduction catalytique du CO2 en consommables chimiques“. Thesis, Université Paris-Saclay (ComUE), 2016. http://www.theses.fr/2016SACLV051/document.
Der volle Inhalt der QuelleFossil resources have been extensively used for the past 200 years allowing a fast paced industrializationin our society. However we are facing today several challenges to preserve our way of life 1) CO2 shouldbe captured and stored/used to avoid large quantity of CO2 to be released in the atmosphere 2) Bypassthe use of fossil resource by using another source of carbon for the synthesis of chemicals 3) Developefficient energy storage technologies to rely more on renewable intermittent energy sources. As CO2 is acheap widely available resource, this waste could be used as well as a source of carbon for the synthesisof value added chemicals but also as a way to store energy in the tandem CO2/MeOH. However as it isan inert gas few processes using CO2 have been industrialized so far.Inspired by Nature’s way to use CO2 we decided to design new reactions from carbon monoxide andformic acid, two derivatives easily available from CO2 that could enable us to overcome the limitationwe faced with CO2. We therefore studied the transformation of CO2 to methanol using formic acid as anintermediate and a reductant and we subsequently used this reaction to perform the methylation ofaromatic amines using formic acid. Finally we developed a new reaction of amines homologation withcarbon monoxide allowing the formation of several C–C bonds
Rus, Yahdi Bin. „Nanocomposites à base de graphène fonctionnalisé pour le stockage de l'énergie et la catalyse“. Thesis, Université Paris-Saclay (ComUE), 2019. http://www.theses.fr/2019SACLN068.
Der volle Inhalt der QuelleAbstract: Functionalized graphene sheets with a ratio C/O~x (FGSx) was further functionalized with a tetrazine derivatives (3,6-bis(2-pyridyl)-1,2,4,5-tetrazine) by inverse demand Diels-Alder cycloaddition reactions. Functionalized FGS20 and FGS13 potential applications were explored on energy storage (super-capacitor) and catalysis (oxygen reduction reaction).In supercapacitor applications, nanocomposites made of functionalized FGS20 with polypyrrole were synthesized in two steps by first incorporating pyridine-pyridazine functions on FGS20 surface through cycloaddition followed by electropolymerization of pyrrole in acetonitrile. The specific capacitance of the material was measured by galvanic charge-discharge cycles and the stability upon cycling investigated in various electrolytic media (acetonitrile, ionic liquid, acidic, and neutral water) in comparison with non-functionalized FGS20 with or without polypyrrole. While acetonitrile reveals pure capacitive behaviour for all investigated mate-rials, acidic water is the medium where the capacitance values are the highest and surprisingly where nano-composites with polypyrrole show better capacitance retention upon cycling than graphene alone. A positive impact of graphene functionalization prior to electropolymerization was demonstrated in all electrolytic media (capacitance losses limited to less than 8% after 1500 cycles in all media but neutral water), highlighting the interest of interface control in this kind of nanocomposites
Rivera, Cárcamo Camila. „Atomes isolés supportés sur des matériaux carbonés pour la catalyse de réactions d'hydrogénation“. Thesis, Toulouse 3, 2020. http://www.theses.fr/2020TOU30174.
Der volle Inhalt der QuelleThis research work focuses on the preparation of carbon-based single atom (SA) catalysts and their applicability on hydrogenation reactions. Chapter 1 correspond to a comprehensive review over experimental and computational studies aiming at: i) preparing SAC on carbon materials, ii) understanding the metal-support interactions in SAC, and iii) studying how this relates to catalytic performances. In Chapter 2 we were able to understand the possibility of producing different Ru@fullerene nanostructures that can be nanometrically modulated by varying the conditions during their synthesis, solvent and Ru/C60 ratio, through well-defined nanoparticles (NP) to very small clusters and even single atoms (SA) with a high metallic loading (~ 6-20wt%). We applied these nanostructures as catalysts in the hydrogenation of nitrobenzene, finding that Ru SA is less efficient than Ru NP, performance that was also studied by DFT calculations. Chapter 3, details a new and straightforward protocol for the creation of vacancies over carbonaceous supports. We propose that is possible to create defects/vacancies over the supports by a controlled subsequent two-steps process, which comprises the subsequent creation and composition of surface oxygen groups. Magnetic characterization reflexed the presence of this reactive species with a paramagnetic behavior raising form possible radicals species on the surface. Afterwards, we showed that was possible to use such defects as anchoring point to successfully stabilize single metallic atoms (Ru, Pd, Pt, Ni, Cu, Co, Ir) with a loading up to ~ 1.6wt%. Also, by improving this method, we arrived to be capable to control the ratio SA/NP for a given metallic loading ranging from 10 to 200. Chapter 4, through a combined experimental-theoretical study, we provide an explanation of the influence of structural characteristics of Pd/C catalysts for alkene hydrogenation. Highly dispersed Pd nanoparticles (PdNP) are necessary to activate dihydrogen. A high concentration of surface defects on the carbon support is necessary to stabilize Pd single atoms (PdSA), which coexist with PdNP on Pd/C catalysts. A high concentration of oxygenated surface groups is also necessary on the carbon support to allow hydrogen spillover. We demonstrate that such combination allows a cooperative catalysis to operate between PdNP and PdSA that involve the formation of PdSA-H species, which are much more active than PdNP-H for alkene hydrogenation but also isomerization. Indeed, for myrcene hydrogenation activity variations of several orders of magnitude were measured as a function of the value of this ratio SA/NP. We show that the control of this ratio allows the development of a new generation of highly active catalysts integrating the ultra-rational use of precious metals in short supply. Finally, Chapter 5, focuses on the catalytic performance of SA catalysts in carbon dioxide hydrogenation. The results show highest activity for Pt as well as 99% selectivity to CO. On the other hand, Ru catalysts had highest selectivity to CH4
Rubulotta, Giuliana. „Catalytic Conversion of Biogenic Substrate into Valuable Building Blocks“. Thesis, Lyon, 2016. http://www.theses.fr/2016LYSE1250.
Der volle Inhalt der QuelleThe goal of this PhD project was in an early stage to study the activities of several commercial metal nanoparticles based catalysts for the mild hydrogenation of limonene. The hydrogenation of limonene has been performed in neat limonene and under mild conditions, e.g. low temperature (30°C) and low molecular hydrogen pressure (3 bar), aiming at a sustainable production route for (+)-p-1-menthene. In our study, the active metal nanoparticles (Pt, Pd and Ru) and supports (carbon, silica and alumina) were systematically varied and tested. It was found that the heterogeneous catalyst Pt/C alongside Pt/Al2O3 under mild reaction conditions (room temperature and 3 bar H2) was highly active and selective in the reduction of R-(+)-limonene to the partial hydrogenation product (+)-p-1-menthene. Moreover, the catalytic activity and stability of Pt/C were maintained during recycling tests under batch conditions and thus allowed the implementation of this catalytic system into continuous flow operation. The selective hydrogenation of terminal C=C bond over the internal one in limonene was rationalized by detailed kinetic studies which revealed an 8-fold difference in reaction rate between the two reactions. This previous study with commercial catalysts gave the possibility to tune the synthesis of heterogeneous metal-based catalysts for the next step of the study, where different heterogeneous metal based catalysts (Pt, Ru, Pt3Sn, and Ni), developed from a colloidal-based approach were tested in the hydrogenation of limonene. Those catalysts contain the same metal loading and similar particle sizes (ca. 2 nm) homogeneously dispersed onto non structured oxides (silica and alumina), carbon, or embedded into the walls or at the pore surface of a mesostructured silica materials (SBA-15). All the catalysts from the Pt series were particularly active in the selective hydrogenation of limonene towards p-menthene with further conversion into p-menthane, showing a very high reaction rate. Among of all those catalysts, the one containing Pt nanoparticles embedded in the walls of the silica showed the highest TOF, of ca. 2200 h-1 after two hours of reaction and a maximum yield in p-menthene of ca. 85 % was obtained after 10 hours of reaction. The same catalyst was tested in a continuous flow system and a stable yield of ca. 80% during 6 hours of reaction was reached. No products of isomerization were detected in the crude mixture during the reaction. We could therefore conclude that, using either a heterogeneous commercial catalyst like Pt/C or using a heterogeneous metal based catalyst developed from a colloidal-based approach like SBA-15{walls}, it was possible to achieve a selective conversion of limonene into p-menthene in batch and in continuous flow conditions
Reboule, Iréna. „Réactions d'aza-Michael en catalyse et catalyse énantiosélective par les iodures de samarium“. Paris 11, 2006. http://www.theses.fr/2006PA112148.
Der volle Inhalt der QuelleAza-Michael additions of aromatic amines to unsatured N-acyloxazolidinones catalyzed by samarium diiodides give precursors of beta-aminoacids. Depending on the substrate and the amine, the Michael adduct Pm can be accompanied with a second product Pa stemmed from a 1,4 addition and an amidation reaction. This last one can be used as a cleavage reaction of N-acyl-oxazolidinones using samarium diiodide in THF. This study was extended to enantioselective catalysis using samarium iodobinaphtholate and Michael adducts were obtained with high enantiomeric excesses up to 88%. An isoinversion phenomenon was observed and the calculated isoinversion temperature was close to the experimental value. A non linear effect was also studied at different temperatures to characterize dimeric species in solution. Several structures were proposed
Martin, Myriam. „Réactions d'aminolyse en catalyse et catalyse énantiosélective par des complexes de terres rares“. Paris 11, 2009. http://www.theses.fr/2009PA112331.
Der volle Inhalt der QuelleThis PhD was focused on the development of the use of rare earths in catalysis and in particular for aminolysis of functionalized meso epoxides and aziridines by aromatic amines. The samarium diiodide is used as a catalyst of Lewis acid type and we have shown that samarium diiodide catalyzes the aminolysis of functionalized epoxides in mild conditions and allowes to isolate various new aminoalcohols despite the presence of an additional heteroatom. Samarium iodo binaphtholate is an efficient catalyst for asymmetric ring opening of epoxides containing different heteroatoms by aromatic amines such as aniline, ortho- or para-anisidine. Many β-aminoalcohols containing heterocycle, not described in the literature before our study, have been isolated with enantiomeric excesses up to 71%. These catalysts were also tested in the aminolysis of activated or no activated aziridines reaction. Various 1,2-diamines have been isolated under mild conditions but with samarium iodo binaphtholate diamines were isolated with low ee in all cases. In order to increase enantiomeric excesses, we have described a synthesis for new complexes of rare earths prepared by a very simple procedure from rare earth chloride, lithium trimethylsilyl and binaphthol. These new complexes are heterobimetallic compounds and complexes of samarium, yttrium, neodymium, scandium and lanthanum were successfully isolated. The complexes of samarium and yttrium catalyzed under mild conditions the aminolysis reaction of functionalized epoxyde. The β-aminoalcohols were prepared with enantiomeric excesses up to 84% in the case of the reaction between the epoxide of 2,5-dihydrofuran and para-anisidine
Jia, Zixian. „Elaboration des matériaux composites nanostructurés Ag, Au/TiO² pour la dépollution des effluents gazeux avec une activation par plasma“. Thesis, Paris 13, 2013. http://www.theses.fr/2013PA132050.
Der volle Inhalt der QuelleDuring this Phd work, we have developed a plasma-catalytic process of acetaldehyde removal using a diphasic process coupling a nano-structured catalyst and an atmospheric pressure plasma. The elaboration of the nanoparticulate catalyst has been firstly studied. Then its performance coupling with plasma has been investigated. The monodispersed titanium-oxo-alkoxy nanoparticles are generated in the sol-gel reactor with turbulent micromixing and deposited onto glass plates or glass balls as monolayer nanocoatings. The silver and gold deposition is achieved by the ions reduction at UV-A light illumination. The photocatalytic growth kinetics and nanoparticle morphology are studied experimentally by the TEM, SEM and AFM methods. It’s also interesting to discuss the mechanism of the nanoparticles formation and evaluate its quantum efficiency. The drawn conclusions are supported theoretically through the calculation of the absorption spectra. Then the efficiency of the process coupling a dielectric barrier discharge and a fluidized nanostructured silver and gold based bed for the degradation of a model pollutant (acetaldehyde CH₃ CHO) is studied. In the first part, the efficiency of the plasma alone process is discussed, in terms of pollutant removal and CO and CO₂ production. In the second part, CH₃ CHO removal as well as COx production is studied as a function of the photocatalytic reduction time of Ag⁺ and Au³⁺ ions, which is related to the deposited silver and gold mass. The pollutant removal pathways, including homogeneous chemistry in the plasma phase and heterogeneous chemistry on the surface, are discussed. Finally, the production of main by-products is presented and compared between Ag and Au catalysts
Ligny, Romain. „Nouveaux (co)polyesters à séquences contrôlées par catalyse de polymérisation stéréosélective“. Thesis, Rennes 1, 2018. http://www.theses.fr/2018REN1S110/document.
Der volle Inhalt der QuellePoly(hydroxyalkanoate)s (PHAs) are biodegradable and biocompatible polyesters of interest for their application in the biomedical field or as alternative to plastics derived from the petroleum industry. The synthesis of PHAs by ring-opening polymerization (ROP) of cyclic monomers, β-lactones, enables a good control of the molar mass, the microstructure and the functionality of the polymers. The properties of the polyesters can be tuned by the using different monomers. In recent decades, various PHAs have been synthesized, in particular poly(hydroxybutyrate) (PHB) and poly(alkyl malolactonate)s (PMLARs). This work has been extended to the ROP a new family of β-lactones, namely 4-alkoxymethlylene-β-propiolatones (BPLORs). Thus, various yttrium-based catalyst systems provide (co)polymers with original tacticity (syndiotactic, atactic or isotactic) and topology (block, alternating or random copolymers). The stereoselectivity of the catalytic systems implemented is unprecedented in the current scientific context. Indeed, the nature of the substituants on the ancillary ligand of the yttrium complexes enables to tune the microstructure and therefore the properties of the resulting PHAs
Tang, Yue. „Catalyse asymétrique en présence de complexes d'or(I) - Un nouvel arsenal pour la construction d'architectures moléculaires“. Thesis, Paris Sciences et Lettres (ComUE), 2019. http://www.theses.fr/2019PSLEC038.
Der volle Inhalt der QuelleOver the last years, gold catalysis has gained considerable significance in organic synthesis, since it comprises atom-economic and highly efficient processes for the transformation of relatively simple substrates into valuable, highly complex molecular architectures. Despite these outstanding advances, the enantioselective variants have not flourished as fast and remain a highly challenging task. This project intends to address some technological barriers and contribute to fundamental research in the field of asymmetric cycloisomerization and domino reactions implying gold(I) and gold(III) catalytic systems, on a first approach, and highly modular chiral carbenic ligands. The ligands will be based on chiral N-Heterocyclic Carbenes (NHCs), as they represent a very effective and robust class of supporting ligands. More specifically, we will focus on the development of highly modular NHC architectures specifically designed to bring the chiral information in close proximity to the metallic center, which represents a key feature for an efficient asymmetric induction in gold catalysis. The target substrates of catalysis will be divided in two main classes, namely the 1,n-enynes and the unsaturated carbonyl/imino derivatives, since their gold(I)- and gold(III)-catalyzed conversion will afford a great molecular complexity. By taking advantage of the different reactivities and catalytic profiles of the NHC-Au(I) and NHC-Au(III) complexes, along with their silver counterparts, this project will allow the elaboration of a complete panel of efficient, general and unprecedented enantioselective catalytic systems towards the preparation of bio-relevant building blocks, precursors of natural products and biologically active molecules
Belarbi, Hichem. „Élaboration des zéolithes nano-structurées M-ZSM-5 (M=Cu, Cr et Fe) : Etude comparée des solides poreux minéraux et organométalliques MOFs dans l’oxydation de méthylènes benzyliques“. Thesis, Montpellier 2, 2014. http://www.theses.fr/2014MON20192.
Der volle Inhalt der QuelleEnergy, sustainable development, and health are at the heart of contemporary concerns of the planet. The inevitable disappearance of fossil fuels, the severe consequences of carbon emissions on the environment and health require quick and effective solutions to supplement the first and minimize others. Among the solutions proposed, there are porous materials which have proven their effectiveness; however, there are still obstacles to be corrected or circumvented. In this thesis, we focus on the problem of bulky molecules' inaccessibility in micro pores of the materials we wish to study. In the first part, we optimize the material in this case, ZSM-5, with a reduction in particle size to a microscopic scale to another nano, which allows us to increase the external surface after changing certain parameters. In the second step, in order to give a catalytic entity to our support (zeolite), we activate with this material incorporating cations selected according to a specific property of the benzyl methylenes oxidation reaction. For this reason we developed different method of preparation. We conclude this thesis by catalysis with M-ZSM-5 (M = Cu, Cr and Fe) and a comparative study on the method of preparation and the MOFs that bears the same cations as mineral part which constitutes the materials
Boreux, Arnaud. „Development of new dual catalysis systems with gold and copper“. Thesis, Université Paris-Saclay (ComUE), 2017. http://www.theses.fr/2017SACLX053/document.
Der volle Inhalt der QuelleDuring the last decades, transition metal catalysis has become an essential tool in organic synthesis. Each year, thousands of publications report the development of new reactions mediated by metal complexes. This manuscript depicts our contribution to this field. The first chapter presents a general comparison of the reactivity of coinage metals (Cu, Ag, Au) complexes in catalysis, with a special focus on their ability to perform electrophilic activation (Au) or nucleophilic transfer (Cu) reactions. Representative examples are given to illustrate these concepts. In the second part of the manuscript, the synthesis of trifluoromethylated allenes and enones by gold(I) catalysis is reported. A general method for the preparation of CF3-allenes has been developed based on a gold(I)-mediated 1,5-hydride shift. The scope and limitations of the method, as well as some subsequent transformations of the products are described. Using similar substrates, a gold(I)-catalyzed [3,3]-acetate rearrangement was applied to the preparation of CF3-enones. The employment of this method into a one-pot procedure involving a subsequent Diels-Alder reaction is also reported. The third part focuses on the copper(I)-catalyzed borofunctionalization of allenes. The recent reports from the literature are reviewed, and our contributions to this area of research are described through the study of a new copper(I)-catalyzed allene boroacylation method. Finally, preliminary results on the elaboration of a copper(I)/gold(I) catalytic one-pot process are presented