The Dong research group is interested in harnessing the power of transition metal catalysis to transform simple molecules and reagents (such as carbon monoxide, hydrogen gas, olefins, and C–H and C–O bonds) into valuable products (such as functionalized heterocycles, chiral carbonyl compounds and natural products). This thesis will describe our continual effort to achieve this goal. Part I describes the Pd-catalyzed functionalization of sp2 and sp3 C–H bonds. Carbon monoxide is used as a stoichiometric reductant in the cyclization of diarylnitroalkenes to afford biologically relevant 3-arylindoles and other N-containing heterocycles with carbon dioxide as the only stoichiometric byproduct. Also, an aryl sulfoxide moiety is shown to direct the arylation of sp3 C–H bonds to afford beta-functionalized amides. Part II describes the Ru-catalyzed sp3 C–O bond activation of alkoxypyridines and related heterocycles. In this transformation, an O- to N-alkyl migratory rearrangement occurs to afford N-alkylated pyridones which are structures found in many natural products and pharmaceutical agents. Part III describes our pursuit of metal-catalyzed asymmetric synthesis. Readily available benzylic bromides are carbonylated with carbon monoxide in alcoholic solvent mixtures. The resulting medicinally relevant 2-arylpropionic esters are obtained with moderate to good enantioselectivities. Preliminary results for the asymmetric hydrogenation of gem-diarylethylenes and novel ligand development are also disclosed. Part IV describes our efforts towards the total synthesis of 6-deoxyerythronolide B. Our retrosynthetic analysis of the macrolide antibiotic involves disconnections at the lactone linkage and between C7 and C8. The two equally complex fragments were prepared via reliable aldol, hydroboration, crotylation and redox chemistry. Rather than the typical macrolactonization method to form the 14-membered ring, we propose an alternative strategy where we plan to cyclize with a metal-catalyzed ring-closing metathesis event. Currently, this step is under investigation by other members in the group.

The Dong research group is interested in harnessing the power of transition metal catalysis to transform simple molecules and reagents (such as carbon monoxide, hydrogen gas, olefins, and C–H and C–O bonds) into valuable products (such as functionalized heterocycles, chiral carbonyl compounds and natural products). This thesis will describe our continual effort to achieve this goal. Part I describes the Pd-catalyzed functionalization of sp2 and sp3 C–H bonds. Carbon monoxide is used as a stoichiometric reductant in the cyclization of diarylnitroalkenes to afford biologically relevant 3-arylindoles and other N-containing heterocycles with carbon dioxide as the only stoichiometric byproduct. Also, an aryl sulfoxide moiety is shown to direct the arylation of sp3 C–H bonds to afford beta-functionalized amides. Part II describes the Ru-catalyzed sp3 C–O bond activation of alkoxypyridines and related heterocycles. In this transformation, an O- to N-alkyl migratory rearrangement occurs to afford N-alkylated pyridones which are structures found in many natural products and pharmaceutical agents. Part III describes our pursuit of metal-catalyzed asymmetric synthesis. Readily available benzylic bromides are carbonylated with carbon monoxide in alcoholic solvent mixtures. The resulting medicinally relevant 2-arylpropionic esters are obtained with moderate to good enantioselectivities. Preliminary results for the asymmetric hydrogenation of gem-diarylethylenes and novel ligand development are also disclosed. Part IV describes our efforts towards the total synthesis of 6-deoxyerythronolide B. Our retrosynthetic analysis of the macrolide antibiotic involves disconnections at the lactone linkage and between C7 and C8. The two equally complex fragments were prepared via reliable aldol, hydroboration, crotylation and redox chemistry. Rather than the typical macrolactonization method to form the 14-membered ring, we propose an alternative strategy where we plan to cyclize with a metal-catalyzed ring-closing metathesis event. Currently, this step is under investigation by other members in the group.

There has been growing interest in two-dimensional (2-D) crystals beyond graphene for next-generation nano-electronics. Transition metal dichalcogenides have been most widely studied, for their semiconducting characteristics and hence, potential applications. This interest has fueled many efforts to establish methods for synthesis of MoS2 layers, a most promising candidate, in controlled numbers over large areas. One of the most scalable methods is chemical vapor deposition (CVD). The current approaches to growth from the vapor phase are by and large very empirical. This thesis is hence concerned with the predictive synthesis of n-layered MoS2 using CVD uniformly over large areas and the correlation of growth parameters with the structural and electronic properties of the deposited films. A simple, relatively non-toxic and non-pyrophoric chemistry, consisting of Mo(CO)6 and H2S was first chosen for vapor phase synthesis. This chemistry allowed synthesis of MoS2 from precursors located outside of the growth reactor, a necessary condition for electronics device technology. Iterative thermodynamic modeling of the Mo-S-C-O-H system and growth was then done to identify the appropriate CVD process windows for the growth of pure MoS2, departures from stoichiometry, contamination and breakdown of equilibrium modelling. Remarkable agreement between theoretical modelling and actual growth has been observed leading to predictable deposition. Within these thermodynamic windows, the gas phase supersaturation were then reduced to obtain better kinetic control over crystal growth. It is shown that control of supersaturation at the very initial stages of growth is critical to reduce the nucleation density and hence obtain monolayers with small defect densities. In addition, it is shown that at higher temperatures the kinetics of nucleation and growth are determined by the supersaturation on the growth surface. Physico-chemical modelling reveals that this steady state supersaturation is determined by the kinetics of adsorption and desorption. All of this understanding has been used to realize a variety of structures from discrete crystalline islands- 30 nm to 150 microns- to deposits with controlled number of layers – n =1 to 6 or greater- uniformly over large areas on quartz and sapphire. Gas phase chemistry also affects the electrical characteristics of the as deposited layers. It is shown, for the first time, that by changing gas phase Mo to S ratios the stoichiometry of the deposited layers MoS2 can be made metal or chalcogen deficient. This yields MoS2 that can be either p-type or n-type. p-type and n-type MoS2 with mobilities up to 7.4 cm2/Vs and 40 cm2/Vs respectively are demonstrated. FETs fabricated on MoS(2-x) samples (increasing x) with varying stoichiometry showed a maximum on-current of 18 μA (4.5 μA/μm) in vacuum and 0.6 μA (0.15 μA/μm) in air for a drain bias Vds = 1 V. Sulphur deficiency also affect reliability. While samples with a higher concentration of sulphur vacancies have higher mobility in vacuum, the mobility degrades significantly in air and gets reversed on annealing in H2S. The details of such correlation between growth and electrical characteristics are discussed in this thesis.

Aliar alta produtividade ao menor custo de processo é o principal desafio econômico de uma Aciaria Elétrica. Para isso, mudanças no processo almejando práticas que resultam em uma maior eficiência do FEA, com um menor custo envolvido, ocorrem constantemente. Este trabalho avalia um processo de FEA, com capacidade de 62 toneladas de aço, operando com carregamento de sucata metálica e ferro-gusa. Dois grupos de corridas de aço, pertencentes à dois cenários distintos, foram estudadas. Os cenários foram denominados Cenário I e Cenário II, sendo que, no segundo cenário ocorreram mudanças nas práticas de injeções de carbono e oxigênio, nas práticas de adição de cales no carregamento e mudanças na quantidade de Sucata Shredder no FEA. O objetivo deste trabalho foi analisar como essas mudanças influenciaram no processo. A composição química de aço e escória de dois padrões de carga (C e E) foi comparada entre os cenários. Verificou-se que a massa de escória diminuiu para os dois padrões de carga. Porém, a basicidade do padrão C foi reduzida de 2,5 para 2,1, enquanto para o padrão E manteve-se em 2,2 para os dois cenários. O MgO de saturação foi avaliado através de diagramas de saturação isotérmicos (ISD), e a maior parte das corridas do Cenário II ficaram acima da linha de saturação da escória. Houve uma redução de 30% do oxigênio injetado para os dois padrões e seus teores de fósforo no aço aumentaram significativamente. No entanto, apenas o padrão C teve uma variação nos teores de carbono no aço. A energia elétrica consumida mostrou-se dependente dos teores de FeO e MgO da escória. O padrão E apresentou um aumento significativo de 10 kWh/t. O rendimento metálico dos padrões C e E aumentou 3,59% e 2,22%, respectivamente. No Cenário II, o aumento da sucata Shredder no carregamento foi duas vezes maior. O Cenário II apresentou uma redução dos teores de cobre no aço para os dois padrões. As quantidades médias de injeção de carbono não tiveram variação significativa, por outro lado, através dos gráficos de distribuição, notou-se uma maior estabilidade nos valores de injeção. Para o padrão E observou-se uma quantidade mínima de ferro na escória para a razão global C/O de 0,75. Uma análise da razão das injeções de carbono e oxigênio durante o refino foi feita. Observou-se uma maior estabilidade das injeções ao longo do tempo de refino para o Cenário II em ambos os padrões. / Combine high productivity and lower costs is the main economical challenge of a steelmaking melt shop. Therefore, changes in the process aiming practices that result in higher efficiency of the EAF, with lower costs, occur frequently. This work evaluates an EAF process, with capacity of 62t of steel, operating with metal scrap and pig iron load. Two groups of steel heats that represents two distinct scenarios were studied. The scenarios were called Scenario I and Scenario II. In the Scenario II carbon and oxygen injection practices, limes loading practice and Shredder scrap loading amount were modified. The aim of the present work is analyze how these changes affected process parameters. The steel and slag chemical composition of two loading patterns (C and E) was compared on the scenarios. It was found that the slag mass reduces for both loading patterns. However, the basicity of the pattern C was reduced from 2.5 to 2.1 while the pattern E was maintained on 2.2 for both scenarios. The MgO saturation content of the slag is evaluated through Isothermal Solubility Diagrams. Most of the heats of the Scenario II MgO content are higher than the minimal saturation content. There was a reduction of 30% of the injected oxygen for both loading patterns and their P content increased significantly. Meanwhile, only the pattern C shows a variation on carbon content in the steel. The electric power consumption showed proportional relation to FeO and MgO content of the slag and the pattern E showed a significant increase of 10 kWh/t. The metallic yield of the patterns C and E increased 3.59 and 2.22, respectively. The scenario II showed a reduction of the Cu content in both patterns. The carbon injection amount means did not vary significantly, but, through distribution graphs, was noted a higher stability in the injection amount. For the E pattern, a minimum amount of iron in the slag was observed for the overall C/O ratio of 0,75. An analysis of the ratio of the carbon and oxygen injection during the refining period was done. It was observed a higher stability of the injections along the refining period for the Scenario II on both patterns.

Aliar alta produtividade ao menor custo de processo é o principal desafio econômico de uma Aciaria Elétrica. Para isso, mudanças no processo almejando práticas que resultam em uma maior eficiência do FEA, com um menor custo envolvido, ocorrem constantemente. Este trabalho avalia um processo de FEA, com capacidade de 62 toneladas de aço, operando com carregamento de sucata metálica e ferro-gusa. Dois grupos de corridas de aço, pertencentes à dois cenários distintos, foram estudadas. Os cenários foram denominados Cenário I e Cenário II, sendo que, no segundo cenário ocorreram mudanças nas práticas de injeções de carbono e oxigênio, nas práticas de adição de cales no carregamento e mudanças na quantidade de Sucata Shredder no FEA. O objetivo deste trabalho foi analisar como essas mudanças influenciaram no processo. A composição química de aço e escória de dois padrões de carga (C e E) foi comparada entre os cenários. Verificou-se que a massa de escória diminuiu para os dois padrões de carga. Porém, a basicidade do padrão C foi reduzida de 2,5 para 2,1, enquanto para o padrão E manteve-se em 2,2 para os dois cenários. O MgO de saturação foi avaliado através de diagramas de saturação isotérmicos (ISD), e a maior parte das corridas do Cenário II ficaram acima da linha de saturação da escória. Houve uma redução de 30% do oxigênio injetado para os dois padrões e seus teores de fósforo no aço aumentaram significativamente. No entanto, apenas o padrão C teve uma variação nos teores de carbono no aço. A energia elétrica consumida mostrou-se dependente dos teores de FeO e MgO da escória. O padrão E apresentou um aumento significativo de 10 kWh/t. O rendimento metálico dos padrões C e E aumentou 3,59% e 2,22%, respectivamente. No Cenário II, o aumento da sucata Shredder no carregamento foi duas vezes maior. O Cenário II apresentou uma redução dos teores de cobre no aço para os dois padrões. As quantidades médias de injeção de carbono não tiveram variação significativa, por outro lado, através dos gráficos de distribuição, notou-se uma maior estabilidade nos valores de injeção. Para o padrão E observou-se uma quantidade mínima de ferro na escória para a razão global C/O de 0,75. Uma análise da razão das injeções de carbono e oxigênio durante o refino foi feita. Observou-se uma maior estabilidade das injeções ao longo do tempo de refino para o Cenário II em ambos os padrões. / Combine high productivity and lower costs is the main economical challenge of a steelmaking melt shop. Therefore, changes in the process aiming practices that result in higher efficiency of the EAF, with lower costs, occur frequently. This work evaluates an EAF process, with capacity of 62t of steel, operating with metal scrap and pig iron load. Two groups of steel heats that represents two distinct scenarios were studied. The scenarios were called Scenario I and Scenario II. In the Scenario II carbon and oxygen injection practices, limes loading practice and Shredder scrap loading amount were modified. The aim of the present work is analyze how these changes affected process parameters. The steel and slag chemical composition of two loading patterns (C and E) was compared on the scenarios. It was found that the slag mass reduces for both loading patterns. However, the basicity of the pattern C was reduced from 2.5 to 2.1 while the pattern E was maintained on 2.2 for both scenarios. The MgO saturation content of the slag is evaluated through Isothermal Solubility Diagrams. Most of the heats of the Scenario II MgO content are higher than the minimal saturation content. There was a reduction of 30% of the injected oxygen for both loading patterns and their P content increased significantly. Meanwhile, only the pattern C shows a variation on carbon content in the steel. The electric power consumption showed proportional relation to FeO and MgO content of the slag and the pattern E showed a significant increase of 10 kWh/t. The metallic yield of the patterns C and E increased 3.59 and 2.22, respectively. The scenario II showed a reduction of the Cu content in both patterns. The carbon injection amount means did not vary significantly, but, through distribution graphs, was noted a higher stability in the injection amount. For the E pattern, a minimum amount of iron in the slag was observed for the overall C/O ratio of 0,75. An analysis of the ratio of the carbon and oxygen injection during the refining period was done. It was observed a higher stability of the injections along the refining period for the Scenario II on both patterns.

Ce travail décrit une méthodologie de synthèse pallado-catalysée en milieu liquide ionique [BMIM][BF4] en utilisant des ligands phosphines et polyphosphines pour les réactions d’alcynylation d’arènes et méthoxylation des alcynes. La première partie de ce mémoire est consacrée à une synthèse et une discussion sur l’aspect « chimie durable » des liquides ioniques en particuliers les sels d’imidazoliums, leur synthèse, et leurs propriétés physico-chimiques. La deuxième partie, concerne un rappel bibliographique sur les réactions de couplage carbone-carbone catalysées par les métaux de transition et en particuliers le palladium en milieu liquide ionique. Dans la troisième partie sont présentés les résultats catalytiques obtenus dans le cas des couplages de bromo et chloroarènes et hétéroarènes avec des alcynes terminaux en milieu [BMIM][BF4]. La quatrième partie est consacrée à la synthèse de ligands originaux de type triphosphines et à la réaction d’alkoxylation catalysée par leurs complexes de palladium en milieu [BMIM][BF4]. / The properties of the ionic liquids such as their low melting point, their non-volatility, their thermal stability, and specially their ability to solubilize organic and inorganic compounds, made of them an interest media for organic synthesis. During this work, two principal research orientations were make it with the aim of the development of an efficient and immobilized palladium catalytic system which opens the way to recycling or continuous flow chemistry. The first part of this work was the study of the Heck alkynylation in [BMIM][BF4], using the system palladium monophosphines (PPh3 or imidazolium monophosphines) to make the coupling of a variety of activated and deactivated bromides and chlorides substrates with different terminal alkyne and diyne. The second part of this work was dedicated to the synthesis of new tiphophines ligand and their palladium complexes and the study of their potential in the methoxylation reaction in [BMIM][BF4].

No description available.

Cette thèse s’inscrit dans le cadre d’un programme de recherche en collaboration avec l’industrie dont l’enjeu est d’utiliser des composites à matrice céramique (CMC) pour la réalisation d’arrière-corps de moteurs pour l’aviation civile.La première partie de ce travail est consacrée à l’étude des fibres de carbure de silicium (Si-C-O) de première génération. Diverses caractérisations physico-chimiques (analyse chimique élémentaire, MEB, MET, spectroscopie Raman, RMN du solide du 29Si et du 13C, DRX…) ont permis d’établir des relations entre la composition chimique, la structure et les propriétés mécaniques des différentes fibres (Nicalon NL série 100 et 200, et Tyranno LoxM, S, ZMI et AM). Une simulation thermodynamique de la phase amorphe intergranulaire SiCxOy a été proposée en s’appuyant sur des données calorimétriques de la littérature obtenues à partir de verres d’oxycarbure de silicium.La seconde partie de ce mémoire est consacrée à l’élaboration par dépôt chimique à partir d’une phase vapeur (CVD) et à la caractérisation de revêtements d’interphase B-C-N. L’influence des conditions d’élaboration (température, pression, composition initiale des gaz) sur la composition chimique des dépôts, leur structure et leur résistance à l’oxydation sous air sec et ambiant a été étudiée. Enfin, les propriétés mécaniques de ces interphases ont été évaluées et des essais de durée de vie ont été réalisés à l’échelle du microcomposite. / This thesis is a part of a research project in partnership with the industry. The aim of the overall project is to design, develop and manufacture exhaust components made of Ceramic Matrix Composites (CMC’s) for civil aircraft engines.The first part of the work deals with the study of first generation silicon carbide fibres (Si-C-O). Various physical and chemical characterizations (quantitative elemental analysis, SEM, TEM, Raman spectroscopy, solid NMR of 29Si and 13C, X-ray diffraction …) were carried out in order to understand the relation between the chemical composition, the structure and the mechanical properties of silicon oxycarbide fibres (Nicalon NL series 100 and 200, and Tyranno LoxM, S, ZMI and AM). Besides, a thermodynamic description of the amorphous SiCxOy phase based on high temperature calorimetry data from the literature is proposed.The second part is devoted to elaboration, by Low Pressure Chemical Vapour Deposition (LP-CVD), and characterization of hexagonal boron carbonitride (B-C-N) coatings. The chemical composition, structure and oxidation resistance (in dry or ambient air) of the coatings were investigated as a function of the deposition conditions (temperature, pressure, initial gas phase composition). Finally, the use of B-C-N coatings as interphases in CMC’s (i.e. their ability to deflect matrix cracks) was investigated by tensile tests on SiC/SiC microcomposites. Their lifetime in static fatigue was also evaluated at 550°C in room atmosphere.

Les analogues de nucléosides sont d'une importance considérable dans la recherche de nouveaux candidats médicaments antiviraux et anticancéreux. La ribavirine est en effet le premier nucléoside triazole antiviral synthétique. Elle est toujours activement utilisée en milieu hospitalier pour le traitement de l'hépatite C et celui des pandémies virales émergentes. Récemment, le besoin de nouveaux agents thérapeutiques efficaces dotés de nouveaux mécanismes d'action a donc créé un regain d'intérêt dans la création de nouvelles entités structurelles de nucléosides triazoles. Au cours de mon doctorat, j’ai été activement engagée dans l’élaboration de nouvelles structures O-arylées et S-arylées de nucléosides triazoles. Les nucléosides triazoles O-arylés ont été obtenus par substitution nucléophile aromatique initiée par micro-ondes, tandis que les nucléosides triazoles S-arylés ont été synthétisés par réaction de couplage C-S en utilisant un catalyseur palladié possédant des ligands mixtes nouvellement mis au point dans notre laboratoire. Le concept du système de catalyseur à ligands mixtes est extrêmement avantageux et enrichissant puisqu’il permet de combiner de façon rationnelle des ligands possédant des fonctionnalités complémentaires afin de promouvoir des réactions avec des substrats pour lesquels ces réactions sont très compliquées. Enfin, afin d'améliorer la solubilité dans l'eau des analogues nucléosidiques triazoles actifs que nous avons identifiés, j’ai tenté de conjuguer le nucléoside triazole à un dendrimère amphiphile dans le but d'élaborer un système de délivrance efficace des médicaments et ainsi d’améliorer leur biodisponibilité. / Nucleoside mimics are of considerable importance in the search of antiviral and anticancer drug candidates. One noteworthy example is ribavirin, the first synthetic antiviral triazole nucleoside discovered 40 years ago, which is still actively in clinic use for treating hepatitis C infection and emerging viral pandemics. Recently, ribavirin has been also reported to demonstrate apoptosis-related anticancer effects and is in clinical trial for treating leukemia. Consequently, there is a renewed interest in creating new structural entities of triazole nucleosides with the aim of developing potent therapeutic agents with novel mechanisms of action. During my PhD program, I have been actively engaged in constructing structurally novel O-arylated and S-arylated triazole nucleosides. The O-arylated triazole nucleosides were obtained via microwave promoted aromatic nucleophilic substitution, whereas the S-arylated triazole nucleosides were synthesized via C-S coupling reaction using our newly developed mixed ligand Pd catalyst (Pd2(dba)3/Xantphos/CyPF-tBu). The concept of the mixed ligand catalyst system is extremely advantageous and rewarding, offering a unique opportunity to rationally combine ligands with complementary features in order to promote the reactions with challenging substrates which are otherwise difficult to proceed. Finally, in order to improve bioavailability of the active triazole nucleoside analogues identified in our group, I have attempted to conjugate the triazole nucleoside to an amphiphilic dendrimer in the view to establishing an effective drug delivery system and offering a better bioavailability.

Cette thèse est divisée en huit chapitres. Les trois premiers chapitres bibliographiques constituent respectivement un rappel des grands principes de la chimie radicalaire, une présentation des possibilités offertes par la chimie radicalaire des xanthates et une revue des méthodes d'allylation radicalaire, principale thématique de nos travaux. Les trois chapitres suivants sont consacrés à des applications d'une méthode d'allylation radicalaire de simples alcools allyliques, récemment découverte au laboratoire. Ces applications nous ont permis de définir des nouvelles voies de synthèse d'éthers d'énols régio-définis, de cétones et dicétones-1,4, de sulfures vinyliques, et enfin d'oléfines fluorées et trifluorométhylées. Les dicétones-1,4 et les sulfures vinyliques obtenus ont en particulier été mis à profit pour la préparation de carbo- et d'hétérocycles fonctionnalisés. Un effet de polarité remarquable a par la suite été découvert pour le processus de fragmentation radicalaire lors de la synthèse d'alcènes trifluorométhylés. Ce dernier a permis le développement d'une nouvelle méthode de synthèse de cétones et de dicétones-1,5 dans laquelle la nouvelle cétone formée provient de la rupture homolytique inusuelle d'une liaison carbone-carbone. Les résultats obtenus sont présenté dans un septième chapitre. Enfin, une nouvelle voie d'accès au alpha-céto carbinols vinyliques, composés à fort potentiel synthétique, est décrite dans un huitième chapitre. Cette méthode exploite le réarrangement sigmatropique de Mislow-Braverman-Evans de sulfoxydes allyliques. Elle constitue l'approche la plus directe au alpha-céto carbinols vinyliques et présente l'avantage de partir de simples cétones.