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1
Huang, Xiaohua 1973. "Palladium-catalyzed C-C, C-N and C-O bond formation." Thesis, Massachusetts Institute of Technology, 2003. http://hdl.handle.net/1721.1/29639.
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Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2003.Vita.
Includes bibliographical references.
New methods for Pd-catalyzed cross-coupling reactions of aryl halides or arenesulfonates are described. Key to the success of these transformations is the proper choice of ligand and reaction conditions. Palladium catalysts supported by bulky, monodentate phosphine ligands with a biaryl backbone or the bidentate ligand, Xantphos, effectively promote the formation of ca-aryl carbonyl compounds. Base-sensitive functional groups are better tolerated when a weak base, such as K3PO4, is used. One of the most difficult transformations in Pd catalysis, the intermolecular C-O bond formation between primary alcohols and electron-neutral or even electron-rich aryl halides, was effectively promoted by the use of a new generation of ligands, 3-methyl-2-di-t-butylphosphinobiaryl. The one-step synthesis of ligands from cheap starting materials, as well as the mild reaction conditions employed for the coupling reactions, enables the practical use of Pd catalysis to access aryl alkyl ethers for the first time. Continuing study of Pd-catalyzed C-N bond-forming processes using biaryl monophosphine ligands led to the discovery of a structural derivative of these ligands, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl. This ligand, in combination with a Pd source, produces a catalyst system with both a greater degree of activity and of stability than those that use our previous ligands. Substrates that were not amenable to Pd catalysis previously are reexamined using this new catalyst system, and excellent results are obtained.
by Xiaohua Huang.
Ph.D.
2
Raghuvanshi, Keshav. "Ruthenium(II)-Catalyzed C-N, C-O and C-C Formations by C-H Activation." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2017. http://hdl.handle.net/11858/00-1735-0000-002B-7D4C-2.
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Voigtländer, David. "Neue Platin-katalysierte C-C- und C-O-Verknüpfungsreaktionen." [S.l. : s.n.], 2001. http://deposit.ddb.de/cgi-bin/dokserv?idn=961741740.
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Qian, Xin. "Cobalt-Catalyzed C-C and C-N Coupling reactions." Phd thesis, Ecole Polytechnique X, 2013. http://pastel.archives-ouvertes.fr/pastel-00943479.
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Ce travail de these a permis le déveloippement de nouvelles reactions de couplage catalysées par des sels de cobalt(II) Le premier chapitre décrit l'allylation cobalta catalysée d'halogénures d'alkyles. La méthode est facile à mettre en œuvre, efficace avec une grande variété d'halogénures d'alkyes et des acétates ou carbonates d'allyle substitués. Les rendements vont de bons à excellents et la tolérance fonctionnelle élevée. Dans le cas d'acétates d'allyle substitués le produit linéaire est obtenu majoritairement ou exclusivement. Quelques expériences ont permis de mettre en lumière la formation d'espèce radicalaire lors du cycle catalytique. Les premiers essais pour étendre cette méthodologie aux couplages allyle-allyle et alkyle-alkyle sont également décrits. Le deuxième chapitre porte sur l'amination catalysée au cobalt d'organozinciques fonctionnalisés en utilisant des N-chloroamines. La procédure est simple et générale et demande des conditions plus douces que celles précédemment décrite, tout en tolérant un très large éventail de substrats, avec une bonne tolérance à de nombreux groupes fonctionnels. Les premiers essais pour étendre la méthodologie à la réaction entre un organozincique et une source électrophile de soufre en vue de former des liaisons C-S sont également exposés. Enfin le dernier chapitre décrit la réaction d'organozinciques engendrés par catalyse au cobalt avec une source " verte " de cyanure électrophile, N-cyano-N-phenyl-p-methyl-benzenesulfonamide (NCTS), pour conduire avec de bons rendements aux arylnitriles correspondants. Des sources analogues de CN+ ont également été testées.
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Luyten, Marcel Andre. "Zur Synthese von (c,c,c,t)-[5.5.5.5]Fenestran /." [S.l : s.n.], 1985. http://www.ub.unibe.ch/content/bibliotheken_sammlungen/sondersammlungen/dissen_bestellformular/index_ger.html.
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Liu, Weiping. "Ruthenium- and Manganese-Catalyzed C−O and C−C Formation via C−H Activation." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2016. http://hdl.handle.net/11858/00-1735-0000-0028-8771-3.
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Fabris, Massimo <1980>. "Innovative green methodologies for C-C, C-N and C-O bond forming reactions." Doctoral thesis, Università Ca' Foscari Venezia, 2011. http://hdl.handle.net/10579/1096.
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In questo lavoro di tesi è riportato l'impiego di alcuni strumenti della Green Chemistry (come la CO2, i liquidi ionici e i dialchilcarbonati) per la messa a punto di metodologie innovative a ridotto impatto ambientale per la formazione di legami C-C, C-N e C-O. Sono state investigate le seguenti reazioni: la metatesi dell'1-ottene catalizzata da sistemi a base di Re ossido, in presenza di CO2 densa come solvente; l'addizione di Michael di nitroalcani e beta-dichetoni a chetoni alfa,beta-insaturi catalizzata da liquidi ionici; la selettiva mono-idrossialchilazione di aniline con la glicerina carbonato, catalizzata da faujasiti; la selettiva bis-N-alchilazione di aniline da parte del dimetilcarbonato prodotto in situ via transesterificazione di carbonati ciclici con metanolo, catalizzata da faujasiti; l'alchilazione di aniline con carbonati ciclici catalizzata da liquidi ionici; la reazione di decarbossilazione dei dialchilcarbonati in presenza di diversi catalizzatori eterogenei; la reazione tra fenolo e glicerina carbonato catalizzata da faujasiti.In this PhD thesis it is presented the use of some Green Chemistry Tools (supercritical carbon dioxide, ionic liquids and dialkylcarbonates) for the set up of new green methodologies for C-C, C-N and C-O bond forming reactions. The following reactions have been investigated: the self-metathesis of 1-octene catalysed by supported Re oxide systems, carried out using dense CO2 as solvent; the Michael addition of nitroalkanes and beta-diketones to alpha,beta-unsaturated ketons catalyzed by task specific phosphonium based ionic liquids; the selective mono-hydroxyalkylation of anilines with glycerol carbonate catalysed by alkali metal exchanged faujasites; the selective bis-N-methylation of anilines carried by dimethylcarbonate prepared in situ via the transesterification of alkylene carbonate with methanol catalysed by alkali metal exchanged faujasites; the alkylation of primary aromatic amines with alkylene carbonates, catalysed by phosphonium based ionic liquids; the decarboxylation reaction of dialkyl carbonates catalyzed by different heterogeneous systems; the reaction of glycerol carbonate with phenol, in the presence of faujasites as catalysts.
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Pagès, Lucas. "Hydrofonctionnalisation d'allénamides terminaux par catalyse au cuivre : formation de liaisons C-C, C-S, C-P et C-O." Electronic Thesis or Diss., Montpellier, Ecole nationale supérieure de chimie, 2022. http://www.theses.fr/2022ENCM0017.
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L'objectif de la thèse consiste à découvrir de nouveaux procédés économiques, non toxiques et non polluants pour réaliser la synthèse de molécules à haute valeur ajoutée (dans le domaine de la pharmacie et des matériaux), à partir de molécules de départ simple pouvant éventuellement être issues directement du monde végétal. Ces nouveaux procédés feront principalement appel à la catalyse homogène et à des catalyseurs métalliques peux coûteux et peu toxiques à base par exemple de cuivre (les méthodes que ces nouveaux procédés sont destinés à remplacer font en général appel à des catalyseurs très coûteux et très toxiques à base de palladium et de ligands sophistiqués). Les recherches reposeront sur l'expertise de l'équipe d'accueil dans le domaine l'hydrofonctionnalisation1 de liaisons insaturées (dont l'hydroamination) ainsi que dans celui de l'arylation de nucléophiles carbonés, oxygénés ou azotés,2 par catalyse au cuivre (formation de liaisons C-C et C-hétéroatome). Le projet comportera une partie méthodologie de synthèse ainsi qu'une partie d'étude mécanistique très poussée sur les systèmes catalytiques découverts (RMN, études cinétique, isolation de complexes métalliques intermédiaires, calculs DFT). L'application et le transfert vers le milieu industriel, domaine dans lequel l'équipe a une très grande expérience, seront alors ensuite envisagés et mis en œuvre s'il y a lieu. 1. a) Chem. Comm, 2015, 51, 11210. b) Org. Lett. 2015, 17, 1224. c) Org. Lett. 2016, 18, 1482. d) Adv. Sytnh. Cat., 2017, 349, 4388. e) ACS. Catal. 2017, 7, 425. f) Org. Lett. 2018, 20, 223. g) Synthesis, 2019, 51, 1225. 2. a) Angewandte Chemie, 2007, 46(6), 934. b) Angew. Chem. Int. Ed. 2009, 48, 337. c) Angew. Chem. Int. Ed. 2009, 48, 6954. d) Angew. Chem. Int. Ed. 2009, 48, 8725. d) Angew. Chem. Int. Ed. 2012, 51, 12815. e) Chem. Comm, 2013, 49, 7412. f) Angewandte Chemie, 2015, 54, 1058. g) Angewandte Chemie, 2016, 55, 3785One of the main objective of the thesis is to discover new economic, non-toxic and non-polluting processes for the synthesis of targets with high added value (in the field of pharmacy and materials), starting from simple starting molecules (possibly issues from the plant world). These new processes will mainly use homogeneous catalysis and inexpensive and low-cost metal catalysts based for example on copper (the methods that these new processes are intended to replace generally make use of very expensive and highly toxic palladium based catalysts and sophisticated ligands). The research will be based on the expertise of the host team in the field of hydrofunctionalization (ref 1) of unsaturated bonds (including hydroamination) as well as in the arylation of carbon, oxygenated or nitrogenous nucleophiles (ref 2) by copper catalysis (formation of C-C and C-heteroatom bonds). The project will include a synthesis methodology part as well as a very advanced mechanistic study of the discovered catalytic systems (NMR, kinetic studies, isolation of intermediate metal complexes, DFT calculations). Application and transfer to industry, where the team has a great deal of experience, will then be considered and implemented if necessary. 1. a) Chem. Comm, 2015, 51, 11210. b) Org. Lett. 2015, 17, 1224. c) Org. Lett. 2016, 18, 1482. d) Adv. Sytnh. Cat., 2017, 349, 4388. e) ACS. Catal. 2017, 7, 425. f) Org. Lett. 2018, 20, 223. g) Synthesis, 2019, 51, 1225. 2. a) Angewandte Chemie, 2007, 46(6), 934. b) Angew. Chem. Int. Ed. 2009, 48, 337. c) Angew. Chem. Int. Ed. 2009, 48, 6954. d) Angew. Chem. Int. Ed. 2009, 48, 8725. d) Angew. Chem. Int. Ed. 2012, 51, 12815. e) Chem. Comm, 2013, 49, 7412. f) Angewandte Chemie, 2015, 54, 1058. g) Angewandte Chemie, 2016, 55, 3785
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Hu, Ying. "C/C++ preprocessing directive analysis." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2001. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp05/MQ65583.pdf.
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Cáceres, Salazar Jorge Cristián, and Acuña Patricio Carreño. "C&C Power Technologies." Tesis, Universidad de Chile, 2015. http://repositorio.uchile.cl/handle/2250/137038.
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Tesis para optar al grado de Magíster en Administración (MBA)Jorge Cáceres Salazar [Parte I], Patricio Carreño Acuña [Parte II]
Patricio Carreño Acuña [Parte II],no envía autorización para acceso a texto completo de su documento.
El presente trabajo consiste en el desarrollo de un plan de negocio para la empresa C&C Power Technologies, cuyo giro corresponde a la provisión de servicios energéticos con el objetivo de aumentar los niveles de eficiencia energética de sus clientes, esto en base a un modelo de negocio ESCO, cuya sigla en inglés significa Energy Services Company. Dentro de la industria de servicios energéticos, las empresas que operan bajo el modelo ESCO se caracterizan principalmente por dirigir íntegramente un proyecto de eficiencia energética en las instalaciones del cliente, incluyendo una auditoría energética, propuestas técnicas, propuestas de financiamiento, instalación y mantenimiento de equipamiento tecnológico y monitoreo de ahorros energéticos logrados. Este modelo de negocio se caracteriza por crear una relación a largo plazo con el cliente, donde los servicios son pagados durante años a través del ahorro monetario generado en base al mayor ahorro energético logrado en los procesos productivos de los clientes. Bajo este modelo de negocios, el cliente normalmente transfiere los riesgos técnicos y financieros a C&C Power Technologies. En relación al sector servicios energéticos a la cual pertenece C&C Power Technologies, este se encuentra inmersa en un contexto en donde los desafíos en el ámbito de la energía a nivel nacional son relevantes. A nivel país estamos frente a múltiples y complejos retos que exigen soluciones eficientes: el crecimiento en la demanda de energía, la dependencia energética, el cambio climático y la expansión del sistema eléctrico, entre otros. Frente a todos estos desafíos, la eficiencia energética surge como una solución factible y sustentable para nuestro país. Al respecto, muchas empresas han comenzado a responder a esta necesidad en dicho ámbito, es así como se ha ido consolidando la industria de servicios energéticos, cuyos esfuerzos se han orientado en alcanzar mayores niveles de eficiencia energética en los diversos rubros económicos. De esta forma, la eficiencia energética es parte de la solución, ya que disminuye el consumo de energía del país, reduce la dependencia de los energéticos importados, aumenta la seguridad de suministro y disminuye las emisiones de gases efecto invernadero. Adicionalmente, contribuye a incrementar la competitividad del país, al haber menores costos de producción. La idea de desarrollar este proyecto nace fundamentalmente como una respuesta a necesidades concretas al interior de las empresas, particularmente en relación al alza sostenido del precio de las distintas fuentes energéticas, lo cual incide directamente en la necesidad de las empresas para bajar sus costos productivos, así como también a la necesidad de lograr mayores niveles de responsabilidad social empresarial, mediante la menor emisión de elementos contaminantes hacia el medioambiente. Los servicios que C&C Power Technologies pretende comercializar en el mercado son: i) auditorías energéticas; ii) consultorías en eficiencia energética, e; iii) implementación de proyectos de eficiencia energética. El modelo de negocios que se quiere implementar en C&C Power Technologies va más allá de limitarse a entregar un diagnóstico energético a sus clientes tal como lo hace la mayor parte de las empresas consultoras en el ámbito de la eficiencia energética establecidas en el país. Este modelo ofrece soluciones prácticas y con un alto valor agregado dado que se ofrece llevar a cabo la dirección integra de proyectos de eficiencia energética, asegurando resultados en términos de ahorros energéticos a ser logrados. Es por esto que el modelo de negocios de C&C Power Technologies posee un mayor atractivo en relación a otros tipos de proyectos que en la actualidad se comercializan en el ámbito de la eficiencia energética, en donde la implementación y monitoreo de los resultados finalmente queda a cargo del cliente. Dentro del plan financiero, se da a conocer el VAN esperado de la empresa, el cual asciende a $418.820.330 (TIR 75,2%). Mediante una simulación de escenarios se demuestra un significativo nivel de sensibilidad del VAN sujeto al cambio en el número de servicios comercializados por la empresa durante los próximos diez años, lo cual da cuenta de que el negocio tiene un nivel de riesgo medio/alto.
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Perry, Ian B. (Ian Brooks). "Transition metal-facilitated C-C and C-F bond forming." Thesis, Massachusetts Institute of Technology, 2017. http://hdl.handle.net/1721.1/112449.
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Thesis: S.B., Massachusetts Institute of Technology, Department of Chemistry, 2017.Cataloged from PDF version of thesis. "June 2017."
Includes bibliographical references.
Chapter 1. Copper-Catalyzed Asymmetric Addition of Olefin-Derived Nucleophiles to Ketones A copper (I) catalyzed coupling olefins and ketones has been developed for the diastereo- and enantioselective generation of homopropargyl alcohols bearing vicinal stereocenters. This method allows for the generation of enantioenriched tertiary alcohols with a high degree of functional group compatibility. The utility of the process is further illustrated by a large scale synthesis with extremely low catalyst loading as well as the late stage modification of several pharmaceuticals. Chapter 2. Copper-Catalyzed Enantioselective Addition of Styrene-Derived Nucleophiles to Imines We describe the catalytic generation of amines bearing vicinal stereocenters with a moderate degree of diastereoselectivity. The stereoselective hydrocupration of an unactivated olefinic component is followed by nucleophilic addition of the organocuprate to an N-phosphinoyl protected imine. The mild and general process tolerates a broad-range of functionality, and the process was shown to be successful at a gram-scale synthesis. Chapter 3. Palladium-facilitated Regioselective Nucleophilic Fluorination of Aryl and Heteroaryl Halides. The preliminary findings regarding an aryl and heteroaryl halide fluorination process facilitated by palladium as a reagent is described. Stoichiometric studies illustrate the utility of the method in producing aryl fluorides with unprecedented regioselectivity, and preliminary studies into the fluorination of five- and six-membered heteroaryl bromides are described. Halogen atom substitution as a route to irreversible oxidative addition of aryl and heteroaryl halides is discussed. This strategy may serve to facilitate the fluorination of particularly problematic heteroaryl bromide and chloride substrates.
by Ian B. Perry.
S.B.
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Zhao, Tony. "Synthesis of functionalized allylic, propargylic and allenylic compounds : Selective formation of C–B, C–C, C–CF3 and C-Si bonds." Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2015. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-116863.
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This thesis is focused on the development of new palladium and copper- mediated reactions for functionalization of alkenes and propargylic alcohol derivatives. The synthetic utility of the 1,2-diborylated butadienes synthesized in one of these processes has also been demonstrated. We have developed an efficient procedure for the synthesis of allenyl boronates from propargylic carbonates and acetates. This was achieved by using a bimetallic system of palladium and copper or silver as co-catalyst. The reactions were performed under mild conditions for the synthesis of a variety of allenyl boronates. Furthermore, the synthesis of 1,2-diborylated butadienes was achieved with high diastereoselectivity from propargylic epoxides. The reactivity of the 1,2-diborylated butadienes with aldehydes was studied. It was found that the initial allylboration reaction proceeds via an allenylboronate intermediate. The allenylboronate reacts readily with an additional aldehyde to construct 2-ethynylbutane-1,4-diols with moderate to high diastereoselectivity. We have also studied the copper-mediated trifluoromethylation of propargylic halides and trifluoroacetates. It was also shown that a transfer of chirality occurred when an enantioenriched starting material was used. In the last part of the thesis, we have described a method for palladium-catalyzed functionalization of allylic C-H bonds for the selective synthesis of allylic silanes. The protocol only works under highly oxidative conditions which suggest a mechanism involving high oxidation state palladium intermediates.At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 1: Accepted.
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Poater, Teixidor Albert. "Isomerism and C-H, C-C, O-O, C-O bond activation studies by transition metals." Doctoral thesis, Universitat de Girona, 2006. http://hdl.handle.net/10803/7939.
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Aquesta tesi és el reflex que de la cooperació entre grups experimentals i grups teòrics s'aconsegueix l'assoliment d'objectius inassolibles de forma individual. A partir de la DFT s'expliquen processos inorgànics i organometàl·lics de gran valor biològic i/o industrial. La tesi està enfocada especialment a l'estudi de complexos mononuclears i binuclears de coure, on té lloc l'activació d'enllaços C-H, C-C, i O-O. L'estudi de complexos octaèdrics de ruteni ha permès dur a terme extensos estudis isomèrics i racionalitzar les propietats espectroscòpiques dels mateixos. A més a més, estudis més puntuals respecte clusters de coure, l'estudi de la reacció de Pawson-Khand, l'estudi d'enllaços Pt-Pt en complexos trimèrics de platí, a més a més de l'estudi de la isomeria de complexos de Ni i Pt.This thesis shows that the cooperation between experimental and theoretical groups gives as a result the achievement of aims impossible working independently. From DFT calculations inorganic and organometallic problems related to great biological and industrial processes can be explained. This thesis is especially focused on the study of mononuclear and binuclear copper complexes, where a C-H, C-C, and O-O bond activation takes place. The study of octahedral ruthenium complexes has allowed carrying out isomeric studies and the rationalization of spectroscopic properties. Furthermore, other little studies related to copper clusters, the Pawson-Khand reaction, Pt-Pt bond interaction in trimer platinum complexes, and isomerism of Ni and Pt complexes.
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Grünberg, Matthias F. [Verfasser], and Lukas [Akademischer Betreuer] Gooßen. "Nachhaltige Konzepte zur C-C, C-N und C-S Bindungsknüpfung / Matthias Grünberg. Betreuer: Lukas Gooßen." Kaiserslautern : Technische Universität Kaiserslautern, 2015. http://d-nb.info/1080521704/34.
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Wrigglesworth, Joseph W. "The development of new palladium(II) catalysed C-C, C-N and C-O bond formations." Thesis, University of Bristol, 2012. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.601218.
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Lee, Kang-sang. "New Concepts and Catalysts for Enantioselective Synthesis of C-C, C-Si, and C-B Bonds." Thesis, Boston College, 2010. http://hdl.handle.net/2345/1739.
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Thesis advisor: Amir H. HoveydaChapter 1. The development of chiral monodentate N-heterocyclic carbenes (NHCs) is presented. Structurally varied twenty-eight new chiral imidazolinim salts, NHC precursors, were synthesized and characterized. Chapter 2. The first example of Cu-catalyzed enantioselective conjugate additions of alkyl- and arylzinc reagents to unactivated cyclic enones is presented. Transformations are promoted in the presence of 2.5-15 mol % of a readily available chiral NHC-based Cu complex, affording the desired products bearing all-carbon quaternary stereogenic centers in 67-98% yield and in up to 97% ee. Catalytic enantioselective reactions can be carried out on a benchtop, with undistilled solvent and commercially available (not further purified) Cu salts. Chapter 3. A new class of enantioselective conjugate addition (ECA) reactions that involve aryl- or alkenylsilylfluoride reagents and are catalyzed by chiral non-C2-symmetric Cu-based NHC complexes are presented. Transformations have been designed based on the principle that a catalytically active chiral NHC-Cu-aryl or NHC-Cu-alkenyl complex can be accessed from reaction of a Cu-halide precursor with in situ-generated aryl- or alkenyl-tetrafluorosilicate. Reactions proceed in the presence of 1.5 equivalents of the aryl- or alkenylsilane reagents and 1.5 equivalents of tris(dimethylamino)sulfonium difluorotrimethylsilicate. Desired products are isolated in 63-97% yield and 73.5:26.5-98.5:1.5 enantiomeric ratio (47%-97% ee). Chapter 4. An efficient Cu-catalyzed protocol for enantioselective addition of a dimethylphenylsilanyl group to a wide range of cyclic and acyclic unsaturated ketones, esters, acrylonitriles and dienones is presented. Reactions are performed in the presence of 1-5 mol % of commercially available and inexpensive CuCl, a readily accessible monodentate imidazolinium salt as well as commercially available (dimethylphenylsilyl)pinacolatoboron. Cu-catalyzed 1,4- and 1,6-conjugate additions afford the enantiomerically enriched silanes in 72%-98% yield and 90:10->99:1 enantiomeric ratio (er) with up to >25:1 of Z:E selectivity. Chapter 5. A Cu-catalyzed method for enantioselective boronate conjugate additions to trisubstituted alkenes of acyclic a,b-unsaturated carboxylic esters, ketones, and thioesters is presented. All transformations are promoted by 5 mol % of a chiral monodentate NHC-Cu complex, derived from a readily available C1-symmetric imidazolinium salt, and in the presence of commercially available bis(pinacolato)diboron. Reactions are efficient (typically, 60% to >98% yield after purification) and deliver the desired boryl carbonyls in up to >98:2 enantiomer ratio (er). In addition, metal-free, nucleophilic activation of a B-B bond has been exploited in the development of a highly efficient method for conjugate additions of commercially available bis(pinacolato)diboron to cyclic or acyclic a,b-unsaturated carbonyls. Reactions are readily catalyzed by 2.5-10 mol % of a simple NHC. A variety of cyclic and acyclic unsaturated ketones and esters can serve as substrates. Transformations deliver boryl carbonyls bearing tertiary as well as quaternary B-substituted carbons in up to >98% yield
Thesis (PhD) — Boston College, 2010
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Chemistry
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Mudarra, Alonso Ángel Luis. "Coinage complexes in C-C and C-N bond-forming reactions." Doctoral thesis, Universitat Rovira i Virgili, 2020. http://hdl.handle.net/10803/670357.
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Els complexos organometàl·lics de coure, plata i or juguen un paper fonamental com espècies reactives
en diverses transformacions químiques. Aquesta tesi aporta coneixement sobre el comportament
d’aquests complexos en la formació d’enllaços C-C i/o C-N. En concret, estudiem: i) el mecanisme de
reacció a través del qual els complexos de coure co-catalitzen un acoblament oxidant en el context de
sistemes bimetàl·lics de rodi i coure; ii) el potencial de nucleòfils de plata com a agents transmetal·lants
en reaccions de trifluorometilació catalitzades per pal·ladi; iii) el mecanisme de reacció de sistemes
bimetàl·lics de Pd/Ag emprant un sistema model; i iv) el comportament de complexos bis(trifluorometil)
cuprat, argentat i aurat com a nucleòfils. En aquesta tesi, on s´han combinat estudis experimentals i
computacionals, s’ha adquirit nou coneixement sobre els processos estudiats, i s’ha contribuït al camp de
la recerca química basada en el coneixement.Los complejos organometálicos de cobre, plata y oro juegan un papel fundamental como especies reactivas en diversas transformaciones químicas. Esta tesis aporta conocimiento sobre el comportamiento de estos complejos en la formación de enlaces C-C y/o C-N. En concreto, estudiamos: i) el mecanismo de reacción por el cual complejos de cobre co-catalizan un acoplamiento oxidante en el contexto de sistemas bimetálicos de rodio y cobre; ii) el potencial de nucleófilos de plata como agentes transmetalantes en reacciones de trifluorometilación catalizadas por paladio; iii) el mecanismo de reacción de sistemas bimetálicos de Pd/Ag usando un sistema modelo; y iv) el comportamiento de complejos bis(trifluorometil) cuprato, argentato y aurato como nucleófilos. En esta tesis, donde se han combinado estudios experimentales y computacionales, se ha adquirido nuevo conocimiento sobre los procesos estudiados, y se ha contribuido al campo de la investigación química basada en el conocimiento.
Organometallic coinage metal complexes are be key reactive species for promoting a wide variety of chemical transformations. This thesis improves the understanding the behavior of these complexes in relevant C-C and/or C-N bond-forming reactions. Specifically, we have explored: i) the mechanistic intricacies of copper species as co-catalyst in the context of rhodium/copper-catalyzed oxidative coupling reactions; ii) the capability of silver nucleophiles as transmetalating agents in palladium-catalyzed trifluoromethylation reactions; iii) the reaction mechanism of Pd/Ag bimetallic reactions using a model system as probe; and, iv) the study of bis(trifluoromethyl) coinage metallates as nucleophiles. The fundamental insights gathered in this Thesis, encompassing both experimental and computational approaches, improve our understanding of the processes under study and make a contribution to the general field of knowledge-driven research in Chemistry.
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Moselage, Marc Philipp. "C-H and C-C Activation by Cobalt and Ruthenium Catalysis." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2017. http://hdl.handle.net/11858/00-1735-0000-0023-3FB2-6.
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Kümpers, Britta Maren Charlotte. "Understanding C₄ leaf development using closely related C₃ & C₄ species." Thesis, University of Cambridge, 2015. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.709247.
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Kanuru, Vijaykumar. "Understanding surface mediated C-C and C-N bond forming reactions." Thesis, University of Cambridge, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.608956.
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Truscott, Fiona Rosemary. "Transition metal catalysed C-C bond formation via C-H functionalisation." Thesis, University of Oxford, 2012. http://ora.ox.ac.uk/objects/uuid:6a1ef296-8d63-470d-96bd-3e01a887c81f.
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The functionalisation of C-H bonds has been widely studied in organic synthesis. This work presents the results of investigation into two areas of current research, copper-catalysed aromatic C-H functionalisation and rhodium-catalysed hydroacylation. Chapter 1 presents the development of palladium- and copper-catalysed aromatic C-H functionalisation with particular attention paid to regiocontrol. Chapter 2 describes the development of copper-catalysed cross-coupling of perfluorinated arenes and alkenyl halides along with efforts to expand this methodology to a more general reaction. In Chapter 3 the development of chelation-controlled rhodium-catalysed hydroacylation is discussed. Chapter 4 outlines the utilisation of amino acid derived N-methylthiomethyl aldehydes in rhodium-catalysed hydroacylation methodology.
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Korvorapun, Korkit. "Site-Selectivity in Ruthenium-Catalyzed C–H and C–C Activations." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2020. http://hdl.handle.net/21.11130/00-1735-0000-0005-148C-7.
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Meggiato, Francesca <1989>. "catalisi micellare nella formazione di legami C-C e C-O." Master's Degree Thesis, Università Ca' Foscari Venezia, 2017. http://hdl.handle.net/10579/10470.
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Rangatia, Janki. "C/EBPalpha downregualtes c-jun expression." Diss., lmu, 2003. http://nbn-resolving.de/urn:nbn:de:bvb:19-10825.
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Thathagar, Mehul Bhupendra. "Nanocluster catalysed C-C coupling reactions." [S.l. : Amsterdam : s.n.] ; Universiteit van Amsterdam [Host], 2006. http://dare.uva.nl/document/18448.
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Oldland, John Rupert. "London clothmaking, c. 1270-c. 1550." Thesis, Royal Holloway, University of London, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.406519.
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This is a business history of clothmaking in London that begins with the earliest surviving records, the city Letter Books and concludes when cloth exports peaked in the 1550's. Towards the end of the thirteenth century London may have been the largest centre for weaving in the country and remained important until the end of the fourteenth century. In the fifteenth century it became the leading centre in the country for fmishing cloth. The city always had a small but successful dyeing industry that became very prosperous at the end of the fifteenth century, before declining in the sixteenth. The study follows clothmaking in London at three levels; the individual craftsman and his work, the six textile craft organizations in the city, the bure1lers, weavers, fullers, shearmen, dyers and, after 1528, the cloth workers , and the textile industry as a whole. The study examines why the individual crafts grew or declined, and how the London industry was affected by structural changes in textile production elsewhere in England and on the continent. It also comments on the way the crafts reacted to the problems they faced. The introduction places London clothmaking in the European and English context, and discusses the significance and purpose of a study on clothmaking in late medieval and early modem London. The first chapter analyses the industry between 1270 and 1340 when the burellers were the most successful textile craft making the' cloth of Candlewick Street', and who then faded with the transition from weaving worsted and serge to woollen cloths. The second chapter examines the growth of woollens' production between 1325 and 1420 and the improving economic position of the weavers and fullers until they succumbed to lower cost rural manufacturers. The third chapter discusses the nature of the work of the cloth fmishers, the fullers and the shearmen, and provides an overview of their growing importance through an analysis of their wills and the alnage records. The fourth chapter studies the dyers throughout the period, but concentrates on their success at the end of the fifteenth century and decline in the early sixteenth century. The fifth chapter covers the growth in numbers, wealth and importance of the cloth finishers, the fullers and shearmen, their internal problems and conflicts with the merchants. The sixth chapter traces the growing mercantile element within the cloth finishing crafts and the events leading up to the amalgamation of the fullers and shearmen as clothworkers in 1528. The seventh chapter examines the first twenty-five years of the clothworkers' company, and specifically explores the mercantile success of its leading members, and the growing wealth and political influence of the company. The thesis concludes with a discussion of the competitive forces that controlled, not just the total industry, but the success or failure of the individual crafts and their members, and provides some observations on the way that the masters and journeymen managed to cooperate, and at times conflicted, in their continual struggle to remain competitive and to provide themselves with a secure livelihood.
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Agee, Laura L. "Sun C to ANSI C converter /." Master's thesis, This resource online, 1995. http://scholar.lib.vt.edu/theses/available/etd-10242009-020128/.
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Stadler, Daniel Eberhard. "Diastereoselektive SN1-artige C-C-Verknüpfungen." München Verl. Dr. Hut, 2009. http://d-nb.info/993731287/04.
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Bollwein, Tobias. "Metallierung, oxidative C-C-Kupplung und C-N-Aktivierung mit Zinkorganyl-Verbindungen." Diss., [S.l.] : [s.n.], 2001. http://deposit.ddb.de/cgi-bin/dokserv?idn=963033077.
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Kulchat, Sirinan. "Dynamic covalent chemistry of C=N, C=C and quaternary ammonium constituents." Thesis, Strasbourg, 2015. http://www.theses.fr/2015STRAF018/document.
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Cette thèse décrit la Chimie Covalente Dynamique (CCD) des échanges imine/imine, Knoevenagel/imine et Knoevenagel/Knoevenagel. La L-proline est un excellent organocatalyseur pour la formation de Bibliothèques Covalentes Dynamiques (BCDs). Cependant, l’interconversion entre des dérivées Knoevenagel de l’acide diméthylbarbiturique et des imines se déroule rapidement sans catalyseur. Une nouvelle classe de CCD basée sur des échanges par substitutions nucléophiles (SN2/SN2’) entre des sels d’ammonium quaternaires et des amines tertiaires est développée, impliquant la catalyse par l’iodure. Les réactions d’échange entre des sels de pyridinium et un dérivé de pyridine génèrent des liquides ioniques dynamiques. Enfin, la sélection cinétique et thermodynamique de la formation d’imines dans la CCD est réalisée en solution aqueuse e ten solvant organiqueThis thesis describes the dynamic covalent chemistry (DCC) of imine/imine, Knoevenagel/imine, and Knoevenagel/Knoevenagel exchange. L-proline is shown to be an excellent organocatalyst to accelerate the formation of dynamic covalent libraries (DCLs). The interconversion between Knoevenagel derivatives of dimethylbarbituric acid and imines is found to occur rapidly in the absence of catalyst. A new class of DCC based on nucleophilic substitution (SN2/SN2’) component exchange between quaternary ammonium salts and tertiary amines is developed, by the use of iodide as a catalyst. The exchange reactions between pyridinium salts and a pyridine derivative generate dynamic ionic liquids. Finally, kinetic and thermodynamic selection of imine formation in a DCC is perfomed in aqueous solution and organic solvent
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Torkelson, Jeffrey Robert. "C-H bond activation and C-C bond formation at adjacent metals." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1998. http://www.collectionscanada.ca/obj/s4/f2/dsk2/ftp03/NQ34848.pdf.
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Catino, Arthur John. "Oxidative C-H and C-C bond functionalization catalyzed by dirhodium caprolactamate." College Park, Md. : University of Maryland, 2006. http://hdl.handle.net/1903/4188.
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Thesis (Ph. D.)--University of Maryland, College Park, 2006.Thesis research directed by: Chemistry. Title from t.p. of PDF. Includes bibliographical references. Published by UMI Dissertation Services, Ann Arbor, Mich. Also available in paper.
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Wang, Hui. "Cobalt(III)- and Manganese(I)-Catalyzed C-H and C-C Activations." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2019. http://hdl.handle.net/11858/00-1735-0000-002E-E5EF-5.
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Desmarchelier, Alaric. "Cascades réactionnelles organocatalysées : création stéréosélective de liaisons C-N et C-C." Versailles-St Quentin en Yvelines, 2012. http://www.theses.fr/2012VERS0031.
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Les travaux exposés dans ce manuscrit ont pour objectif l’étude de cascades réactionnelles organocatalysées permettant de former stéréosélectivement des liaisons C-N, et C-C. Plusieurs approches « one-pot » séquentielles ont été développées à partir de substrats simples, conduisant à des produits hautement fonctionnalisés. Le premier chapitre se focalise sur la formation énantiosélective d’aziridines portant un centre quaternaire, à partir d’énals α-substitués. La difonctionnalisation en position α d’aldéhydes a ensuite été étudiée par double activation énamine. Le deuxième chapitre traite ainsi d’une séquence réaction de Mannich/amination électrophile sur l’acétaldéhyde, pour accéder à des diamines vicinales. Le troisième chapitre décrit la cascade réaction de Michael/amination électrophile, conduisant à la formation d’hydrazinoaldéhydes possédant un centre quaternaire. Enfin, le dernier chapitre se concentre sur l’amination électrophile d’aldéhydes α,α-disubstitués, et son application en cascade organocatalysée pour former des hétérocycles azotés, les 3-pyrrolines, portant un centre quaternaireThe work presented in this manuscript aims at the study of organocascade reactions enabling the stereoselective formation of C-N and C-C bonds. Several sequential one-pot approaches yielding highly functionalized products from simple substrates have been developed. The first chapter describes the enantioselective synthesis of aziridines from α-substituted enals. α-difunctionalization of aldehydes has then been studied via double-enamine activation. The second chapter presents a one-pot Mannich reaction/electrophilic amination of acetaldehyde, leading to vicinal diamines. The third chapter studies a Michael reaction/electrophilic amination cascade, giving rise to hydrazinoaldehydes bearing a quaternary stereocenter. Finally, the last chapter focuses on the electrophilic amination of α,α-disubstituted aldehydes, and its application in an organocascade reaction, leading to 3-pyrrolines with a quaternary stereocenter
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Pardue, Daniel B. "Computational Studies of C–H/C–C Manipulation Utilizing Transition Metal Complexes." Thesis, University of North Texas, 2015. https://digital.library.unt.edu/ark:/67531/metadc801892/.
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Density Functional Theory (DFT) is an effective tool for studying diverse metal systems. Presented herein are studies of a variety of metal systems, which can be applied to accomplish transformations that are currently difficult/impossible to achieve. The specific topics studied utilizing DFT include: 1) C–H bond activation via an Earth-abundant transition metal complex, 2) C–H bond deprotonation via an alkali metal superbase, 3) and amination/aziridination reactions utilizing a CuI reagent. Using DFT, the transformation to methanol (CH3OH) from methane (CH4) was examined. The transition metal systems studied for this transformation included a model FeII complex. This first-row transition metal is an economical, Earth-abundant metal. The ligand set for this transformation includes a carbonyl ligand in one set of complexes as well as a phosphite ligand in another. The 3d Fe metal shows the ability to convert alkyls/aryls to their oxidized counterpart in an energetically favorable manner. Also, “superbasic” alkali metal amides were investigated to perform C—H bond cleavage. Toluene was the substrate of interest with Cs chosen to be the metal of interest because of the highly electropositive nature of this alkali metal. These highly electrophilic Cs metal systems allow for very favorable C—H bond scission with a toluene substrate. Finally, the amination and aziridination of C–H and C=C bonds, respectively, by a CuI reagent was studied. The mechanism was investigated using DFT calculations. Presently, these mechanisms involving the use of coinage metals are debated. Our DFT simulations shed some insight into how these transformations occur and ultimately how they can be manipulated.
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Wolfe, John P. (John Perry) 1970. "Late transition metal catalyzed C-N and C-C bond forming reactions." Thesis, Massachusetts Institute of Technology, 1999. http://hdl.handle.net/1721.1/9521.
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Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1999.Includes bibliographical references.
New methods for the palladium-catalyzed amination of aryl halides are described. Key to these is the development of new catalysts and reaction conditions for these transformations. Initially, P(o-tol)3 ligated palladium catalysts were investigated but gave way to systems that used chelating phosphine ligands which substantially expanded the scope of the catalytic amination methodology. Palladium catalyst systems based on BINAP ((2,2'-diphenylphosphino)-1, 1 '-binaphthyl) allowed for the transformation of a much wider range of amines and aryl halide substrates, as well as aryl triflates. Of practical significance was that the use of cesium carbonate as a base at 100 °C substantially increased the functional group tolerance of the method. Palladium catalysts supported by novel, bulky, electron-rich phosphine ligands are exceptionally effective in the C-N, C-0, and C-C coupling procedures. For some substrate combinations, these palladium catalysts are effective for the room-temperature catalytic amination of aryl chlorides. These palladium catalysts are also highly effective for Suzuki coupling reactions of aryl bromides and chlorides at room temperature. Suzuki coupling reactions of aryl bromides and aryl chlorides are effective at very low catalyst loadings (0.000001-0.005 mol % Pd for ArBr, 0.02-0.05 mol % for ArCI) at 100 °C, and reactions of hindered aryl halides or boronic acids are effected at moderate catalyst loadings (1 mol % Pd). The high reactivity of these catalysts towards aryl chlorides challenges the conventional dogma that chloride substrates cannot be transformed under mild conditions with palladium catalysts, and significantly expands the pool of substrates available for cross-coupling chemistry.
by John P. Wolfe.
Ph.D.
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Midya, S. P. "Transition metal catalyzed (de) hydrogenative C-C and C-N bond formation." Thesis(Ph.D.), CSIR-National Chemical laboratory, Pune, 2018. http://dspace.ncl.res.in:8080/xmlui/handle/20.500.12252/4568.
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Hachicha, Mohamed. "Regulation of C-C and C-X-C chemokine gene expression in synovial fibroblasts and peripheral blood neutrophils." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1996. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp04/NQ25241.pdf.
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Chudasama, V. "The use of aerobic aldehyde C-H activation for the construction of C-C and C-N bonds." Thesis, University College London (University of London), 2011. http://discovery.ucl.ac.uk/1324525/.
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This thesis describes a series of studies directed towards the use of aerobic aldehyde C-H activation for the construction of C-C and C-N bonds by the process of hydroacylation. Chapter 1 provides an introduction to the research project and an overview of strategies for hydroacylation. Chapter 2 describes the application of aerobic aldehyde C-H activation for the hydroacylation of vinyl sulfonates and sulfones. A discussion on the mechanism of the transformation, the effect of using aldehydes with different oxidation profiles and the application of chiral aldehydes is also included. Chapter 3 describes the functionalisation of γ-keto sulfonates with particular emphasis on an elimination/conjugate addition strategy, which provides an indirect approach to the hydroacylation of electron rich alkenes. Chapters 4 and 5 describe the application of aerobic aldehyde C-H activation towards the hydroacylation of α,β-unsaturated esters and vinyl phosphonates, respectively. An in-depth discussion on the mechanism and aldehyde tolerance of each transformation is also included. Chapter 6 describes acyl radical approaches towards C-N bond formation with particular emphasis on the synthesis of amides and acyl hydrazides.
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Straccia, Marco. "C/EBPß and C/EBPß in neuroinflammation." Doctoral thesis, Universitat Autònoma de Barcelona, 2012. http://hdl.handle.net/10803/96887.
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La neuroinmunología estudia la relación entre el sistema inmune y el sistema nervioso. Sus orígenes se remontan a la última década del siglo diecinueve, pero sólo recientemente está en pleno auge. El continuo aumento de la incidencia de las enfermedades neurológicas, especialmente en los países de ingresos altos, ha resaltado la importancia de la clínica de la neuroinflamación. Señales endógenas y/o exógenas anormales pueden determinar el inicio del proceso neuroinflamatorio, el cual representa una respuesta fisiológica pleiotrópica del sistema inmune innato del sistema nervioso central (SNC) que puede ser seguida por la activación del sistema inmune periférico. Los astrocitos y en particular la microglía son las células efectoras del sistema inmune en el SNC. En las últimas décadas se han evidenciado varias funciones de la glía, como la regulación de la trasmisión sináptica o como reservorio celular de la neurogénesis en el cerebro adulto. Aun así, una de las principales funciones de la glía es la de mantener la homeostasis del parénquima del SNC, regulando el microambiente y tamponando eventuales cambios. Cuando la homeostasis del SNC está comprometida más allá de los niveles de tolerancia fisiológica, los astrocitos y la microglía experimentan profundos cambios para restablecer las condiciones necesarias para una óptima actividad neuronal. Este proceso es conocido como activación glial. Esta tesis doctoral se centra en la activación glial, la cual representa un aspecto fundamental de la neuroinflamación. La activación glial es un proceso complejo y altamente relacionado con varios aspectos del sistema inmunológico del SNC y para una mejor comprensión del mismo se introducirán los aspectos fundamentales que lo componen. La activación glial es un cambio importante en la fisiología de la glía, representando profundos cambios del transcriptosoma y de su regulación fina. Hasta ahora han sido descritos diferentes factores de transcripción como reguladores de la transcripción génica durante la activación glial pro- y anti-inflamatoria. Esta tesis estudia la activación glial pro-inflamatoria y en particular el papel de dos miembros de la familia de factores de transcripción de las CCAAT Enhancer Binding Proteins (C/EBPs), los factores C/EBPβ y C/EBPδ. A través de análisis bioinformáticos, bioquímicos y de biología celular, se han caracterizado los promotores de genes dianas de C/EBPβ y C/EBPδ durante la activación glial in vitro. El uso de ratones deficientes en C/EBPβ o C/EBPδ para cultivos primarios de glía mixta y para un modelo de inflamación in vivo han permitido demonstrar la importancia fundamental de estos dos factores en la activación glial. El presente trabajo demuestra claramente cómo C/EBPβ y C/EBPδ interaccionan con los promotores de algunos de los principales genes pro-inflamatorios y cómo la ausencia de uno de los dos determina una reducción de la expresión de los mRNA y de las proteínas de los genes diana. Además, se demuestra que C/EBPβ y C/EBPδ regulan la neurotoxicidad de la microglía in vitro. Finalmente se demuestra que los mismos factores pueden regular la expresión de genes pro-inflamatorios en un modelo in vivo de neuroinflamación. Esta tesis determina el importante papel de los factores de transcripción C/EBPβ y C/EBPδ en la activación glial, evidenciándolos como posibles dianas farmacológicas en el tratamiento terapéutico de la neuroinflamación para prevenir los efectos perjudiciales de la activación glial.Neuroimmunology studies the relationship between immune and nervous system. It originated in the last decade of the 19th century with Santiago Ramón y Cajal work, but only recently it has exploded as an active research topic. The increase incidence of neurological disorders, especially in high-income countries, has pointed out one of the main clinical aspects of neuroimmunology, the neuroinflammation. Abnormal endogenous and/or exogenous signals can cause neuroinflammation which represents a pleiotropic physiological response initiated by the central nervous system (CNS) innate immunity arm and sometimes mediated by the adaptive peripheral arm. Astrocytes and especially microglia are the immune cell effectors in the CNS. In the last decades many functions of glial cells have been shown, such as adult neurogenesis reservoir or constitutive players in neuronal synaptic transmission. However, one of the main glial roles is to maintain the homeostasis in the adult nervous system by supporting neuronal activity, regulating the microenvironment and buffering any disturbances. When CNS homeostasis is compromised over a physiological threshold, astrocytes and microglia undergo enormous phenotypical changes when attempting to reestablish the original environmental state. This process is known as glial activation. This thesis focuses on glial activation. Since glial activation is highly interconnected with several aspects of immune physiology of CNS, many features of nervous-immune system will be briefly introduced. Glial activation causes a marked change in glial cell physiology, resulting in a profound reorganization of transcriptional machinery and its fine regulation. So far, several transcription factors have been described to control glial activation during pro- and anti-inflammatory response. This thesis focus on the transcriptional regulation of pro-inflammatory glial activation and particularly the role of two members of Ccaat Enhancer Binding Protein family (C/EBPs), the transcription factors C/EBPβ and C/EBPδ. Through bioinformatic, biochemical and cell biology analyses we have characterized transcriptional targets of C/EBPβ and C/EBPδ during glial activation in vitro. In vitro mixed glial cultures and in vivo models of C/EBPs deficient mice have been used to demonstrate the key role of C/EBPβ and C/EBPβ in glial activation, especially in activated microglia. This thesis clearly demonstrates that C/EBPβ and C/EBPδ interact with key pro-inflammatory gene promoters and their absence reduces mRNA and protein levels of target genes in glial activation. In addition, it is shown that C/EBPβ and C/EBPδ control the neurotoxic potential of microglia in vitro. Gene expression analysis of systemically LPS-treated knockout mice has also shown an in vivo C/EBPs transcriptional role in brain cortex neuroinflammation. This work demonstrates for the first time the important role triggered by C/EBPβ and C/EBPδ in glial activation, highlighting these transcription factors as potential therapeutic targets to reduce the detrimental consequences of neuroinflammation.
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Javanbakhti, Reza, and Jimmy Pesola. "Statisk detektering av minneshanteringsfel i C/C++." Thesis, Karlstad University, Division for Information Technology, 2006. http://urn.kb.se/resolve?urn=urn:nbn:se:kau:diva-408.
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Det här examensarbetet är baserat på idéer ur ett uppdrag från företaget Saab Aerotech men är ett eget arbete.
Målet var att undersöka om det finns behov av ett verktyg som statiskt kan detektera dynamiska minneshanteringsproblem, som till exempel minnesläckage, i applikationer skrivna i C/C++. På grund av att minneshanteringsfel i C/C++ länge har varit ett känt problem undersökte vi detta och de befintliga lösningarna till det.
Vi fann två metoder till lösningar som de flesta verktyg använde sig av; statisk och dynamisk detektering. De flesta verktyg löste problemet genom att dynamiskt detektera minnesläckor och andra brister som till exempel buffer overflows. Ett verktyg löste dock problemet genom att statisk detektera minneshanteringsfel i källkoden för applikationerna. Eftersom alla befintliga lösningar har någon form av ineffektivitet så har vi undersökt möjligheten att utveckla ett mer effektivt verktyg. Vi har kommit fram till att denna möjlighet finns men det kräver enormt mycket tid och arbete att göra ett komplett verktyg som detekterar minneshanteringsfel statiskt.
Vår prototyp detekterar dynamiska minneshanteringsproblem i källkoden statiskt. Vi har använt oss av hjälpverktygen Flex och Bison för att utveckla vår prototyp av verktyget. Prototypen kan analysera källkod skriven i programspråken C och C++ och klarar att detektera minnesläckage, felaktiga avallokeringar av minne, dangling pointers, samt läsning från och skrivning till ogiltiga minnesområden. På grund av tidsbrist har vi i nuläget inte implementerat något stöd för klasser och objekt i prototypen.
This bachelor’s project is our own project, but it is based on ideas from an assignment from the Saab Aerotech company.
The goal was to investigate if there is a need for a tool that statically can detect dynamic memory management errors, such as memory leaks, in applications written in C/C++. Since the problem of memory management errors in the C/C++ languages has been known for a long time, we decided to investigate this and the existing solutions.
We found that most tools used two methods as solutions; static and dynamic detection. Most of these tools solve the problem by dynamically detecting memory leaks and other deficiencies such as buffer overflows. However, one of these tools used static detection of these deficiencies by scanning the source code of the applications. Since all the existing solutions have some kind of inefficiency, we have investigated the possibility to develop a more efficient tool. We concluded that this is possible but it will take a lot of time and effort to implement a complete tool that statically detects memory management errors.
Our prototype statically detects dynamic memory management problems in the source code. We have used the tools Flex and Bison to develop our prototype of a static detection tool. The prototype analyzes source code written in the programming languages C and C++ and is capable of detecting memory leaks, invalid deallocations of memory, dangling pointers and reading from and writing to invalid memory areas. Currently, due to lack of time, we have not implemented any support for classes and objects in the prototype.
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Brown, Anthony Joseph. "Anglo-Irish Gallicanism, c.1635 - c.1685." Thesis, University of Cambridge, 2004. https://www.repository.cam.ac.uk/handle/1810/251908.
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This thesis explores the development of Gallican and anti-papalist ideas among English and Irish Catholics in the period c. 1635 - c. 1685. It identifies a set of arguments concerning political theology and the rule of faith which, it maintains, constituted a comprehensive response to the dilemmas faced by Catholics living under protestant rulers and trying to reconcile their religious and political loyalties. It suggests that the qualitative identity between the arguments of the writers under consideration is such that it is useful to think in terms of a discrete school of thought which may be labelled 'Anglo- Irish Gallicanism'. The writers whose works are examined in detail are Sir Kenelm Digby, Thomas White (also known as Blacklo), Henry Holden, Hugh Paulin (in religion, Serenus) Cressy, John Austin, Richard Bellings, Redmund Caron and Peter Walsh. This study complements earlier research into English and Irish Catholic thinking in the seventeenth century. Whereas previous discussions of the Oath of Allegiance controversy have been restricted to the period ' c. 1606 - c. 1615, this account stresses the ongoing importance for English and Irish, Catholics of the Oath of Allegiance, and of the issues which it raised, during the rest of the century. The 'Blackloist' contribution to the rule of faith debates has been examined recently, and there have been short studies of aspects of the careers of the other writers, but there has not been a sustained examination of the political theology of the English and Irish Catholics in general or of these writers in particular. Nor has there been any attempt to consider the links between, and coherence of, many of their political-theological ideas and their arguments concerning the rule of faith. This thesis therefore addresses one aspect of the neglected intellectual history of English and Irish Catholics in this period. It is argued that Anglo-Irish Gallican political theology comprised dualist, and even 'Marsilian', accounts of the relationship between the church and the state, and tolerant attitudes towards the relationships between different Christian denominations. These positions were maintained on the basis of anti-papalist rules of faith. Such rules of faith were important not only in debates between Catholics and protestants about the identity of the true church, but also in debates between Catholics and Catholics about the status and teachings of this church. These approaches enabled the writers whose works are analysed to define the status of their religion, and the jurisdictions of their temporal and spiritual leaders, in such a way that they could express absolute loyalty to their temporal sovereigns while still subscribing to what they saw as the true Catholic faith. In these approaches, they built on comparable claims about the papal deposing power advanced during the Oath of Allegiance controversy in the period up to c. 1615; but they systematised these claims and bolstered them with more sustained accounts of political theology and the rule of faith than are evident in the earlier writings. The potential political significance of Anglo-Irish Gallicanism is also noted. Whereas previous accounts of 'popery and politics' in this period have usually been concerned with 'anti-popery and politics', and have paid only scant regard to the ideas and beliefs of the Catholics themselves, this thesis notes that the Anglo-Irish Gallicans played a potentially significant role in the Stuart count during the 1660s and 1670s. In addition to using a range of published material, it draws on manuscript sources written by English and Irish Gallicans concerning the establishment of a tolerant system of government in England and Ireland and the reunion of the English and Roman Churches. These manuscripts were written by, or associated with, English and Irish Gallicans at the heart of the Stuart polity, namely Serenus Cressy and Richard Bellings. Although it cannot consider the purely 'political' role of these Catholics, this thesis is intended to provide some account of the intellectual culture which they represented and which has hitherto been largely ignored. It may therefore have implications for the political history of the Stuarts, as well as for the English and Irish Catholics, in the seventeenth century and later.
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Clark, Felicity Helen. "The Northumbrian Frontiers c.500 - c.850." Thesis, University of Oxford, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.519757.
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Brown, Dearg Sutherland. "Anomeric C-C bond formation via sulphones." Thesis, Imperial College London, 1991. http://hdl.handle.net/10044/1/46687.
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Webster, Paul. "King John's piety, c.1199 - c.1216." Thesis, University of Cambridge, 2007. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.612999.
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Marsland, Rebecca Louise Katherine. "Complaint in Scotland c.1424- c.1500." Thesis, University of Oxford, 2014. http://ora.ox.ac.uk/objects/uuid:05468bd1-c936-426f-9ab4-79afb94a59fb.
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This thesis provides the first account of complaint in Older Scots literature. It argues for the coherent development of a distinctively Scottish complaining voice across the fifteenth century, characterised by an interest in the relationship between amatory and ethical concerns, between stasis and narrative movement, and between male and female voices. Chapter 1 examines the literary contexts of Older Scots complaint, and identifies three paradigmatic texts for the Scottish complaint tradition: Ovid’s Heroides; Boethius’s De Consolatione Philosophiae; and Alan of Lille’s De Planctu Naturae. Chapter 2 concentrates on the complaints in Oxford, Bodleian Library MS Arch. Selden. B. 24 (c. 1489-c. 1513). It considers afresh the Scottish reception of Lydgate’s Complaint of the Black Knight and Chaucer’s Anelida and Arcite, and also offers original readings of three Scottish complaints preserved uniquely in this manuscript: the Lay of Sorrow, the Lufaris Complaynt, and the Quare of Jelusy. Chapter 3 focuses on the relationship between complaint and narrative, arguing that the complaints included in the Buik of Alexander (c. 1438), Lancelot of the Laik (c. 1460), Hary’s Wallace (c. 1476-8), and The Buik of King Alexander the Conquerour (c. 1460-99) act as catalysts for narrative movement and subvert the complaint’s traditional identity as a static form. Chapter 4 is a study of complaint in Robert Henryson’s three major works: the Morall Fabillis (c. 1480s); the Testament of Cresseid (c. 1480-92); and Orpheus and Eurydice (c. 1490-2), and argues that Henryson consistently connects the complaint form with the concept of self-knowledge as part of wider discourses on effective governance. Chapter 5 presents the evidence that a text’s identity as a complaint influenced its presentation in both manuscript and print witnesses. The witnesses under discussion date predominantly from the sixteenth century; the chapter thus also uses them to explore the complaints’ later reception history.
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El, Ayoubi Rami. "Dérivés doublement liés de l'étain et de l'antimoine : stannènes, stannaallènes, stibènes et stibaallènes >Sn=C<, >Sn=C=C<, -Sb=C< et -Sb=C=C<." Toulouse 3, 2008. http://thesesups.ups-tlse.fr/298/.
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Les résultats présentés dans ce mémoire portent sur l'étude de dérivés doublement liés de l'antimoine -Sb=C< et -Sb=C=X (X = C, P) et de l'étain >Sn=C< et >Sn=C=X (X = C, P). Dans le domaine de l'antimoine, nous avons décrit la synthèse de plusieurs précurseurs des hétéroalcènes et des hétéroallènes cibles. Un 1,3-distibacyclobutane, dimère potentiel d'un stibène, a pu être obtenu et caractérisé par spectrométrie de masse et RMN 1H. Les essais d'obtention de stibaallènes et de phosphastibaallènes ont montré qu'il est nécessaire d'utiliser des substituants très encombrants pour avoir des dérivés stables, sans toutefois qu'ils ne le soient trop afin de ne pas empêcher le couplage entre les entités phosphorées et stibiniques. Dans le domaine de l'étain, un stannène stable a été préparé, à savoir Tip2Sn=CR2, grâce à un encombrement stérique important à la fois côtés étain et carbone. Les caractéristiques physicochimiques montrent qu'il s'agit d'un véritable hétéroalcène. Ce stannène s'est révélé très réactif vis-à-vis des dérivés carbonylés ou des diènes. Nous avons décrit plusieurs précurseurs d'espèces alléniques de l'étain (stannaallènes >Sn=C=C< et phosphastannaallènes >Sn=C=P-). Nous avons caractérisé un distannirane qui pourrait provenir d'une réaction de cycloaddition du stannaallène cible Tip2Sn=C=CR2 avec le stannylène issu de sa décompositionThis thesis describes the results obtained in the field of doubly-bonded derivatives of antimony -Sb=C<, -Sb=C=X (X = C, P) and tin >Sn=C<, >Sn=C=X (X = C, P). In the field of antimony, the synthesis of some precursors of such heteroallenes was described. A 1,3-distibacyclobutane, potential precursor of a stibene -Sb=C<, has been characterized. The attempts to obtain stibaallenes and phosphastibaallenes showed that a very large steric hindrance was necessary on antimony and carbon. In the field of tin, the new stable stannene Tip2Sn=CR2 was obtained and stabilized owing to a very large steric hindrance both on Sn and C. This stannene which appeared a true heteroallene according to NMR and X-ray data, was extremely reactive, particularly towards carbonyl compounds and dienes. Some precursors of stannaallenes >Sn=C=C< and phosphastannaallenes -P=C=Sn< have been prepared. A distannirane, obtained by reaction between the stannaallene Tip2Sn=C=CR2 and the stannylene Tip2Sn, was isolated
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Lee, Alison Victoria. "Catalyst and methodology development for regioselective C-N and C-C bond formation." Thesis, University of British Columbia, 2007. http://hdl.handle.net/2429/31377.
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The related investigations of catalytic hydroamination as a key step in synthetic methodology development and the synthesis of new hydroamination catalysts are reported in this thesis. The first section focuses on methodology development for the application of a bis(amidate)bis(amido) titanium hydroamination precatalyst towards the synthesis of functionalized small molecules via a tandem C-N, C-C bond forming reaction sequence. The development of two tandem sequential reactions will be described, as well as their applications in the synthesis of α-cyanoamines, α-amino acid derivatives, β-amino alcohols, diamines, imidazolidinones, and β-amino acid derivatives. These tandem reactions show an expanded substrate scope and increase synthetic flexibility by allowing for alternative starting materials in the preparation of highly functionalized small molecules. The second section describes progress towards the development of an asymmetric tandem reaction sequence, including investigations into the mode of activation for the tandem reaction. It has been established that a nucleophilic activation mode is required to generate an active species for the C-C bond forming step. Furthermore, it is postulated that the coordination environment and steric congestion about the activator impacts reaction efficiency and stereoselectivity. This information will be valuable in the design of future generations of activators. The final section reports the development of two novel group 4 metal complexes for catalytic hydroamination. The synthesis and full characterization of these complexes will be described, as well as the results of the catalytic investigations. Through this investigation it has been postulated that while a change in the electronic nature of the metal complex does enhance catalytic reactivity, the degree of orbital overlap between the ligand and the metal center is also an important consideration in the design of electrophilic hydroamination precatalysts. Hydroamination catalysis is currently an attractive area of intense research. The work in this thesis has demonstrated the use of hydroamination catalysis in the synthesis of highly functionalized small molecules, and has furthered the fundamental understanding of the hydroamination reaction. This increase in understanding can then be applied towards the rational design of more powerful hydroamination catalysts and further their application in the synthesis of functionalized N-containing compounds.Science, Faculty of
Chemistry, Department of
Graduate
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Fleser, Angelica. "Resténose et expression des proto-oncogènes, c-myc, c-fos et c-jun." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1997. http://www.collectionscanada.ca/obj/s4/f2/dsk2/ftp03/NQ35590.pdf.
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Graczyk, Karolina. "Iron- and Ruthenium-Catalyzed Site-Selective C–C Forming Direct C–H Functionalizations." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2015. http://hdl.handle.net/11858/00-1735-0000-0022-5FA5-4.
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