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Msutu, Ath'enkosi. "New methodology for the organocatalysed α-Amination reaction." Doctoral thesis, University of Cape Town, 2015. http://hdl.handle.net/11427/16608.
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Includes bibliographical referencesResearch into organocatalyzed asymmetric reactions has been a rapidly growing and competitive field in recent times, wherein amino catalysis is widely used for the asymmetric functionalisation of carbonyl compounds. Since its simultaneous publication by List and Jørgensen, the organocatalysed α-amination reaction has become a key method for asymmetric heteroatom functionalisation of carbonyl compounds. Herein we report the first application of this methodology to acetals, with the ultimate goal of applying the methodology to the asymmetric desymmetrisation of bis-acetals as a novel contribution to this growing field. Following extensive optimisation, acidic reaction conditions for the reaction were established in which dibenzyl azodicarboxylate (DBAD) was used as the aminating agent and (S)-(-)-5-(2-pyrrolidinyl)-1H-tetrazole as the preferred organocatalyst. The desired aminated products were obtained in high yields and enantioselectivities. The reaction showed broad substrates cope in its application to ketals, dioxolanes and lactols. A hydrazide N-N bond cleavage methodology was also developed for the aminated products in oxazolidinone form. This methodology is based on Magnus' alkylation / E1CB strategy. The novel contribution here is using ditheyl bromoacetate as an alkylating agent and as a better elimination partner. A range of bis-acetals were synthesised via three synthetic routes using malonate-, sulfone and cyclopentene-based synthesis strategies. The acetal reaction was used for the desymmetrisation of two of these bisacetals as a proof of concept. This is a feat not achieved with the more reactive dicarbonyl analogue.
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Atkinson, Duncan. "Novel methods for allylic amination by an intramolecular nitroso ene reaction." Thesis, Loughborough University, 2013. https://dspace.lboro.ac.uk/2134/14069.
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C-H functionalisation reactions aim for the selective cleavage of C-H bonds, and formation of a new carbon or heteroatom bond, often with the use of a transition metal catalyst. These reactions offer potential for functionalisation of hydrocarbons in fewer steps than conventional methods, and with high atom efficiency. They are therefore a subject of intense research in organic synthesis. Carbon-heteroatom bond forming reactions are particularly sought after, and useful in the efficient synthesis of many biologically significant groups such as oxazolidinone rings, 1,2 or 1,3 amino alcohols and amino acid analogues. An efficient, cheap and robust method for C-H amination would also be adaptable to varied syntheses of important large molecules. The necessity for complex and efficient transformations with a minimal number of steps means that heteroatom ring closures are also attractive and widely used reactions in such large molecule syntheses. The nitroso group is a highly reactive species which is normally generated in situ by oxidation of a hydroxylamine, for carbon-nitrogen bond forming reactions including the nitroso Heteroatomic Diels Alder reaction, nitroso ene reaction, and nitroso aldol reaction. Nitroso group reactions often show high stereo- and regioselectivity, and have formed key components of the syntheses of important biological molecules. Enantioselectivive protocols for the nitroso-ene reaction and, to a lesser extent, the nitroso HDA reaction, are poorly developed, however, and the range of available intramolecular nitroso reactions is limited. We aimed to establish efficient single-step intermolecular C-H amination reactions, to give 1,2 and 1,3 heteroatom functionalised molecules, and to develop the capacity for enantioselective induction in this reaction, if possible. Having synthesised a model set of unsaturated hydroxycarbamates, we identified a suitable system for nitroso generation, using a catalytic metal and stoichiometric oxidant. This resulted in in situ generation of cyclised product, with the olefin functionality intact. This cyclisation was then optimised and used to obtain a range of new heterocycles. The possibility of enantioselective induction via chiral catalysts was explored, as well as catalytic systems to increase the stereoselectivity of the reaction. In summary, a cheap, novel and reliable method was developed for formation of oxazolidinone rings from unsaturated hydroxycarbamates using an original intramolecular nitroso ene reaction, and a range of unsaturated heterocycles were synthesised in fairly good yields. Distereoselectivity of the nitroso ene cyclisations was optimised. However, to-date, we were unable to develop an enantioselective varient of the reaction. Several related aminations, as well as transformations of N-hydroxyoxazolidinone products, were also attempted during the project.
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Payard, Pierre-Adrien. "Mechanistic studies of metal-catalyzed reactions : predicting tools for reaction optimization." Thesis, Paris Sciences et Lettres (ComUE), 2019. http://www.theses.fr/2019PSLEE009/document.
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Cette thèse est consacrée à l’étude de mécanismes de réactions catalysées par des métaux ainsi qu’au développement de nouveaux outils pour la rationalisation et la prévision du comportement catalytique. L’étape de transmétallation entre le bore et le nickel a été étudiée en détail à l’aide de méthodes expérimentales variées (electrochimie, RMN, cinétiques) et par DFT, permettant d’expliquer certaines limitations rencontrées par les experimentateurs. La seconde partie de cette thèse est dédiée à la rationalisation du comportement d’une famille d’acides de Lewis : les sels de triflate et de triflimidate. Leur comportement a été étudié sur des réactions modèles d’amination et d’oxidation et une nouvelle échelle théorique d’acidité de Lewis basée sur l’estimation du transfert de charge vers l’acide à permis de reproduire et prévoir l’activité catalytiqueIn this thesis mechanistic studies of metal-catalyzed reactions as well as development of new tools to predict and rationalize the catalytic properties are presented. The boron-tonickel transmetalation step was thoroughly studied by experimental technics (electrochemistry, NMR, kinetics) and DFT calculations, allowing us to solve some of the limitation encountered by the synthetic chemists. In the second part of this thesis the behavior of a family of Lewis acids (triflates and triflimides) is rationalize. Two model reactions (SN and redox) were studied and a new theoretical scale of Lewis acidity was developed based on the charge transferred to the acid allowing us to reproduce and predict the catalytic activity of these salts
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Bassili, Victor Antoine. "Catalytic amination of 1-methoxy-2-propanol : reaction pathway and kinetic modelling /." Zürich, 1991. http://e-collection.ethbib.ethz.ch/show?type=diss&nr=9351.
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Zhang, Yin. "Backbone decoration of imidazol-2-ylidene ligands with amino groups and their application in palladium catalyzed arylative amination reaction." Thesis, Toulouse 3, 2015. http://www.theses.fr/2015TOU30109/document.
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Ce travail s'inscrit dans le cadre de la chimie des carbènes N-hétérocycliques (NHC) et s'articule autour de la fonctionnalisation directe de l'hétérocycle des l'imidazol-2-ylidènes par substitution formelle d'un ou deux groupements diméthylamino. Deux nouvelles catégories de NHCs ont d'abord été obtenues par cette stratégie, dénommées 4-(diméthylamino)imidazol-2-ylidène IArNMe2 et 4,5-bis(diméthylamino)imidazol-2-ylidène IAr(NMe2)2. Les sels d'imidazolium précurseurs de ces NHCs, à savoir le triflate de 4-(diméthylamino)imidazolium (IArNMe2)·HOTf et le triflate de 4,5-bis(diméthylamino)imidazolium (IAr(NMe2)2)·HOTf, ont été synthétisés en couplant la formamidine disubstituée correspondante avec le N,N-diméthyl-chloroacétamide et le 1,2-dichloro-1,2-bis(diméthylamino)éthylène généré in situ respectivement. La quantification des propriétés électroniques des deux nouveaux NHCs a été réalisée à l'aide des complexes de type [Rh(IMes(NMe2)xCl(CO)2], montrant que la donation électronique des ligands NHCs augmente séquentiellement par la décoration avec un ou deux groupements diméthylamino, tandis que les propriétés de p-rétrodonation des NHCs ne sont que légèrement influencées. Par la suite, les complexes de palladium Pd-PEPPSI-IPrNMe2 et Pd-PEPPSI-IPr(NMe2)2 (PEPPSI : Pyridine Enhanced Preparation Purification Stabilization and Initiation) ont été préparés par des voies de complexation classiques. Les propriétés stériques des ligands a été évaluée par la mesure du pourcentage de volume occupé (%Vbur), et il est apparu que les propriétés stériques de ces deux nouveaux ligands NHCs sont également accrues. Les activités catalytiques des deux pré-catalyseurs ont été évaluées en amination de type Buchwald-Hartwig et comparées avec celle de la référence Pd-PEPPSI-IPr. Le pré-catalyseur Pd-PEPPSI-IPr(NMe2)2 s'est révélé le plus actif en amination des chlorures d'aryle à température ambiante. Il constitue également le catalyseur Pd-NHC le plus efficace et le plus général connu à ce jour en permettant de réaliser l'amination des chlorures d'aryle avec une charge de catalyseur très faible (jusqu'à 50 ppm), ou à l'aide d'une base faible telle que le carbonate de césium, et même d'activer les tosylates d'aryle, substrats beaucoup plus difficiles que les chlorures d'aryle . Afin de rationaliser au mieux les effets observés en catalyse en termes de propriétés stéréoélectroniques des ligands NHCs, le squelette arrière aminé des imidazol-2-ylidènes a été dérivatisé plus avant, soit en augmentant la contrainte stérique du groupe NMe2 dans IAr(NMe2) en ciblant le ligand IAr(NiPr2), soit en remplaçant formellement un des groupes amino par un groupe éléctro-attracteur tel un halogène dans le ligand IAr(NMe2)2. Alors que le sel d'imidazolium (IArNiPr2)·HOTf a été synthétisé suivant la même méthode que (IArNMe2)·HOTf, l'halogénation oxydante du squelette d'arrière de (IArNMe2)·HOTf par du NCS ou du NBS a donné les sels (IArNMe2, X)·HOTf avec de très bons rendements dans des conditions très douces. Il convient de noter que cette réactivité originale a été également observée sur les complexes de rhodium(I) et le palladium(II) du ligand IAr(NMe2). Les influences électroniques et catalytiques de ces modifications ont été étudiées de la même façonThis work is incorporated within the framework of the chemistry of N-Heterocyclic Carbenes (NHCs) and aims at functionalizing the skeleton of imidazol-2-ylidenes by attachment of one or two amino groups. Two new NHC classes were first obtained by this strategy, namely the 4-(dimethylamino)imidazol-2-ylidene IArNMe2 and the 4,5-bis(dimethylamino)imidazol-2-ylidene IAr(NMe2)2. The synthesis of the precursors of these NHCs, the 4-(dimethylamino)imidazolium triflates (IArNMe2)·HOTf and the 4,5-bis(dimethylamino)imidazolium triflates (IAr(NMe2)2)·HOTf is based on the coupling between the corresponding disubstituted formamidine and either an a-chloroacetamide for the mono-amino derivative or a reactive dichlorodiaminoethene for the bis-amino analogue. The electronic properties of the resulting new NHCs ligands have been studied by measurement of their Tolman Electronic Parameter (TEP) values obtained from the IR spectra of the complexes [Rh(IMesXY)Cl(CO)2] and by 77Se NMR spectroscopy of their corresponding selenoureas [(IMesXY)=Se]. It was shown that the electronic donation of the carbenic carbon sequentially increases by decoration with one or two amino groups respectively whereas the p-accepting properties of the NHC are only slightly or even not affected by the adjunction of the NMe2 groups on the imidazolyl backbone. Later, the synthesis of the two new PEPPSI-type palladium pre-catalysts PEPPSI-Pd-IPrNMe2 and Pd-PEPPSI-IPr(NMe2)2 were successfully achieved. From the calculated the percent buried volume %Vbur which is related to the steric properties of the two supporting NHC ligands, it appeared that grafting one amino group onto the backbone already leads to significant improvement of steric congestion while the second amino only results in a slight increase of the steric issue. The catalytic efficiencies of both pre-catalysts were evaluated in the benchmark Buchwald-Hartwig amination and compared with this of the reference PEPPSI-Pd-IPr. The bis-aminated pre-catalyst Pd-PEPPSI-IPr(NMe2)2 was shown to be the most active and stable pre-catalyst, and it was shown to be also highly efficient in more challenging amination reaction. It indeed allows to carry out the amination of aryl chlorides at low catalyst loadings or by using a mild base such as cesium carbonate, and even to activate the aryl tosylates, which are more difficult substrates than aryl chlorides. In order to study the critical stereoelectronic properties of the NHC ligands for the efficiency of the corresponding catalysts, further derivatization of the heterocyclic backbone was carried out, either by increasing the bulkiness of the mono-amino group from dimethylamino to diisopropylamino group to generate the carbene IArNiPr2, or by formally replacing one dimethylamino group by an halogen X in the bis-aminoimidazo-2-ylidene to give the carbenes IArNMe2,X. While the imidazolium salts (IArNiPr2)·HOTf was synthesized following the same method as (IArNMe2)·HOTf, the oxidative halogenation of the backbone of (IArNMe2)·HOTf with a N-halosuccinimide afforded (IArNMe2,X)·HOTf in good yields under very mild conditions. Noteworthy, this original reactivity was also observed on the rhodium and palladium complexes of this ligand
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Esposito, Oriana. "Mechanistic and kinetic studies on aryl and alkyl amination reaction catalysed by palladium n-heterocyclic carbene complexes." Thesis, University of Sussex, 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.487117.
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Several studies have been carried out to establish the sequence of intermediates in the catalytic cycle for amination of aryl halides. I ,2 The mechanism suggested by Cloke and Caddick group for the catalytic amination of aryl chloride employing [Pd(NRC)2l as precatalyst (NRC = ·N-heterocyclic carbene), proposed a neutral, 12-electrons mono-ligated Pd(NHC) species as the active intermediate.3 The isolation of a series of (ItBu)2Pd(R-aryl)chloride complexes (ltBu = 1,3-di-tert-butylimidazol-2-ylidene) allowed for kinetic studies hence leading to a mechanistic understanding of the I oxidative addition step, confirming that it occurs by a dissociative mechanism. The subsequent step in the amination catalytic cycle, namely, the dissociation of a carbene and coordination of an amine was investigated and the results are presented in this thesis, and an array of (ItBu)Pd(amine)(R-aryl)chloride complexes were isolated and fully characterized. Kinetic studies were undertaken in order to identify the rate determinig step of the transamination reaction. Moreover, the electronic properties of the para-substituents (R) on the aryl groups of the (ItBu)2Pd(R-aryl)chloride complexes were found not only to influence the rate of the oxidative addition reaction, but also to affect the carbene displacement by the amines. Parallel research based on the understanding of the mechanism of oxidative addition of alkyl halides to the Pd(NHC)2 species have been undertaken, and the synthesis of (ItBu)Pd(neopentyl)chloride (trans isomer) and (IPr)Pd(neopentyl)chloride (cis isomer) (IPr = 1,3-Bis(2,6-Diisopropylphenyl)imidazol-2-ylidene) were. accomplished. Reactivity of these· two complexes was tested toward amines, revealing the significant influence ofN-substituents on the stability of the resulting compounds, and highlighting a possible barrier concerning the achievement of a Pd-catalysed alkyl amination reaction. The oxidative addition of (trimethylsilyl)methyl iodide to Pd(ItBu)z complex was investigated for comparison to the oxidative addition reactions of alkyl halides to the same palladium complex. The unexpected resultant complex, Pd(CHzltBu)zlz, was subjected to DFT study by Dr. Hazari to confirm the zwitterionic nature of the ligand. Kinetic study was conducted on the oxidative addition of TMSI to Pd(ItBu)z to reveal the occurrence of pre-dissociation of one ligand before the addition ofTMSI to yield the [(ItBu)Pd(TMS)(J.t-I)]z.
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Badiei, Yosra Mohammed. "Copper carbenes and nitrenes capture of elusive intermediates and the development of a copper catalyzed C-H amination reaction /." Connect to Electronic Thesis (CONTENTdm), 2009. http://worldcat.org/oclc/458487923/viewonline.
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Mora, Anne-Sophie. "Élaboration de revêtements époxy pour contact alimentaire à empreinte environnementale réduite A perspective approach on the amine reactivity and the hydrogen bonds effect on epoxy-amine systems vanillin-derived amines for bio-based thermosets synthesis of biobased reactive hydroxyl amines by amination reaction of cardanol-based epoxy monomers synthesis of pluri-functional amine hardeners from bio-based aromatic aldehydes for epoxy amine thermosets cardanol-based epoxy monomers for high thermal properties thermosets." Thesis, Montpellier, Ecole nationale supérieure de chimie, 2019. http://www.theses.fr/2019ENCM0012.
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Les travaux de thèse présentés sont issus d’une collaboration industrielle avec la société Nouvelle Sogatra, spécialisée dans la conception, la fabrication et la commercialisation de revêtements de protection bi-composants répondant aux normes d’alimentarité. L’objectif principal de ce projet est de proposer de nouveaux revêtements époxydiques performants en utilisant des produits biosourcés et, dans l’idéal, moins dangereux pour l’Homme et pour l’environnement. Ces travaux de thèse s’axent autour de l’identification de nouvelles méthodologies de synthèse de durcisseurs aminés biosourcés qui soient facilement applicables industriellement.L’amination directe des groupements époxy par ouverture de cycle en présence d’ammoniaque ainsi que l’amination réductrice via la synthèse d’imine ont été sélectionnées comme voies de synthèse pour leur facilité d’application et leur caractère respectueux de l’environnement. Pour cela, des précurseurs commerciaux biosourcés et/ou à toxicité réduite ont été sélectionnés. De nouveaux durcisseurs aminés ont été synthétisés à partir de bio ressources telles que la vanilline, le cardanol et le benzaldéhyde. Ces durcisseurs ont ensuite été utilisés pour la synthèse de système époxy-amine thermodurcissables dont les propriétés physico-chimiques et thermodynamiques ont été caractériséesThe presented PhD works were initiated by an industrial collaboration with the company Nouvelle Sogatra, specialized in the design, manufacturing and marketing of two component protective coatings for food contact. The aim of this project is to offer new high-performance epoxy thermosets from bio based reactants and, ideally with a low impact on the health and the environment. This PhD works focus on the identification of new synthesis methodologies of bio-based amine hardeners, which could be easily industrialized.The direct epoxy amination by ring opening using ammonia and the reductive amination via imine synthesis were selected as synthesis routes for their simple utilization and their eco friendly character. Hence, bio based and/or reduced toxicity commercial precursors were selected. New amine hardeners were synthesized from bio resources, such as vanillin, cardanol and benzaldehyde. These hardeners were then used to synthesize epoxy-amine thermosets, whose thermomechanical and physicochemical properties were characterized
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Colin, Olivier. "Plateforme pyridylalkylamine modulable : un outil pour la catalyse." Thesis, Versailles-St Quentin en Yvelines, 2015. http://www.theses.fr/2015VERS023V/document.
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Les travaux exposés dans ce manuscrit s’articulent autour de l’élaboration de nouvelles plateformes pyridylalkylamines polyfonctionelles et chirales afin de permettre le développement d’un nouveau processus de réactions catalysées en cascade. La première partie de ce document décrit la synthèse de plateformes pyridylméthylamines (pma) portant des motifs chiraux et (thio)urées. La seconde partie traite de leur utilisation dans des réactions d’organocatalyse et de métallocatalyse asymétriques, puis dans des réactions catalysées en cascade séquencée. La troisième partie porte sur la synthèse de plateformes pyridyléthylamines (pea) via l’utilisation d’une réaction d’amination électrophile organocatalysée et une réaction de cyclisation de PrinsThe works described in this manuscript is dealing with the construction of new polyfunctional chiral pyridylmethylamine (pma) platforms in order to allow the development of new one-pot catalytic reaction sequences. The first part of this document focuses on the synthesis of pyridylméthylamine platforms carrying chiral motifs and (thio)ureas. The second part reports their use in asymmetric organocatalysis and metallocatalysis and then in catalyzed cascade reaction sequences. The third part deals with the synthesis of pyridyléthylamine (pea) platforms through an organocatalyzed electrophilic reaction followed by a Prins cyclisation
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Del, Castillo Fernández Estefanía. "Applications of the Hofmann-Löffler reaction for C-H functionalization in Total Synthesis." Doctoral thesis, Universitat Rovira i Virgili, 2020. http://hdl.handle.net/10803/670691.
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Aquesta tesi doctoral representa alguns avenços en el camp de la funcionalització d’enllaç C-H alifàtics. És necessari el desenvolupament de nous mètodes per a la funcionalització selectiva en molècules orgàniques. Per portar a terme aquestes estratègies, els radicals de nitrogen semblen perfectes candidats per generar selectivament enllaços de C-X en posicions no activades. Aquests radicals de nitrogen han estat usats com a intermedis reactius en química sintètica en les darreres dècades, portant a cap la química de transferència d’àtoms d’hidrogen, on la coneguda reacció de Hofmann-Löffler va ser pionera. El primer projecte està basat en el concepte de reacció de Hofmann interrompuda per a l’halogenació selectiva de molècules orgàniques. Per això, vam usar sulfonamides y èsters de sulfamats com a grups dirigents de processos de 1.5 i 1,6 de transferència d’àtoms d’hidrogen per generar radicals centrats en carboni en posicions γ o δ. Aquests radicals son atrapats per àtoms d’halògens donant accés a compostos orgànics amb múltiples halògens en la seva estructura com a estructures cícliques i acícliques. En alguns casos, halogenació veïnal o geminal va ser observada. La segona i tercera part de la tesi aquesta relacionada amb l’ús de la reacció de Hofmann-Löffler per a la formació de l’anell de pirrolidina en alcaloides. La combinació de iode hipervalent amb quantitat catalítica de iode va ser una bona estratègia per a l'aminació en l'última etapa de la síntesi enantioselectiva de la nicotina. Per últim, en la tercera part de la Tesis demostra que aquesta metodologia podria aplicar-se a molècules més complexes podent sintetitzar l’estructura del hasubanan de forma enantioselectiva on la formació de pirrolidina es produeix en els darrers passos de la síntesi.Esta tesis doctoral representa algunos avances en el campo de la funcionalización de enlace C-H alifáticos. Es necesario el desarrollo de nuevos métodos para la funcionalización selectiva en moléculas orgánicas. Para llevar a cabo estas estrategias, los radicales de nitrógeno parecen perfectos candidatos para generar selectivamente enlaces de C-X en posiciones no activadas. Estos radicales de nitrógeno han sido usados como intermedios reactivos en química sintética en las últimas decadas, llevando a cabo la química de transferencia de átomos de hidrógeno, donde la conocida reacción de Hofmann-Löffler fue pionera. El primer Proyecto esta basado en el concepto de reacción de Hofmann interrumpida para la halogenación selectiva de moléculas orgánicas. Para ello, empleamos sulfonamidas y esteres de sulfamatos como grupos dirigentes de procesos de 1.5 y 1,6 de transferencia de átomos de hidrógeno para generar radicales centrados en carbono en posiciones γ or δ. Estos radicales son atrapados por átomos de halógenos dando acceso a compuestos orgánicos con múltiples halógenos en su estructura como estructuras cíclicas y acíclicas. En algunos casos, halogenacion vecinal o geminal fue observada. La segunda y tercera parte de la tesis esta relacionada con el uso de la reacción de Hofmann-Löffler para la formación del anillo de pirrolidina en alcaloides. La combinación de yodo hipervalente con cantidad catalítica de yodo pareció ser una buena estrategia para la aminación en la última etapa de la síntesis enantioselectiva de la nicotina. Por último, en la tercera parte de la Tesis demostramos que esta metodología podría aplicarse a moléculas más complejas pudiendo sintetizar la estructura del hasubanan de forma enantioselectiva donde la formación de pirrolidina se produce en los últimos pasos de la síntesis.
This doctoral Thesis summarizes advances in the field of C-H functionalization of aliphatic bonds. Methods for remote functionalization are necessary to expand the transformations available in the organic molecules. For this transformation, nitrogen-centered radicals are the perfect candidates to promote selective C-X bond formation over unactivated and distal C-H bonds. Nitrogen-centered radicals have been widely used as reactive intermediates in synthetic chemistry in the last decades, carrying out hydrogen atom transfer chemistry, where the well-known Hofmann-Löffler reaction was pioneering. The first research project is based on the concept of ‘interrupted Hofmann-Löffler’ reaction to the selective halogenation of organic molecules. For that, we employed sulfonamides or sulfamates esters as directing/protecting group of the transformation. These directing groups promote 1,5 or 1,6-hydrogen atom transfer generating the carbon-centered radical at γ or δ-positions. This radical is trapped by the addition of a halogen atom at this position. This protocol provided access to multiple halogenated organic compounds, such as cyclic and acyclic structures. In some cases, vicinal and geminal halogenation is observed. The second and the third part of my doctoral Thesis is related to the application of the Hofmann-Löffler reaction for the formation of the pyrrolidine ring into some alkaloids. The combination of hypervalent iodine(III) species with catalytic amount of molecular iodine seemed to be a robust tool for late-stage amination in the enantioselective synthesis of nicotine. In this regard, in the last part of the Thesis we demonstrated that this methodology could be applied to more complex molecules being able to synthesize the enantioselective hasubanan core where the pyrrolidine formation occurred in the last steps of the synthesis.
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Nocquet, Pierre-Antoine. "Vers la synthèse d'une nouvelle classe d'iminosucres conformationnellement contraints : ouverture d'azétidines, cyclisation 4-exo-trig et C-H amination catalytique." Thesis, Strasbourg, 2013. http://www.theses.fr/2013STRAF047/document.
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De précédentes études dans notre groupe ont montré que l'α-1-C-nonyl-1,5-didésoxy-1,5-imino-D-xylitol était un inhibiteur puissant de la β-glucocérébrosidase, enzyme impliquée dans la maladie de Gaucher. Il a été supposé que la conformation chaise inversée de ce composé pouvait expliquer en partie sa forte affinité avec la glycosidase cible. L'objectif ce travail de thèse était la synthèse d'une nouvelle classe d’iminosucres, basée sur un squelette 1-azaspiro[3.3]heptane, possédant deux cycles à 4 membres, analogue conformationnellement contraint de notre "lead" en série iminoxylitol. La première stratégie de synthèse envisagée a permis de mettre en avant une nouvelle réaction tandem d'ouverture d'azétidines conduisant à des spirocyclopropyl γ-lactames. La seconde stratégie testée a conduit dans un premier temps à la formation hautement stéréosélective d'un cyclobutane tétrasubstitué par une réaction radicalaire induite par le SmI2 − permettant ainsi la synthèse des premiers exemples de carbasucres à 4 membres − puis à la formation du carbone azaspiranique de notre cible par une réaction de C-H amination catalysée par des complexes de rhodiumPrevious studies in our group has shown that α-1-C-nonyl-1,5-dideoxy-1,5-imino-D-xylitol was a strong inhibitor of β-glucocerebrosidase, the enzyme involved in Gaucher disease. It was supposed that the inverted chair conformation of this compound could partially explain its high affinity with the target glycosydase.The goal of this PhD work was the synthesis of a new class of iminosugars based on 1-azaspiro[3.3]heptane structures, as conformationally strained analogues of our lead in the iminoxylitol series. During the course of our synthetic study, new azetidine ring-opening tandem reaction leading to spirocyclopropyl γ-lactames has been discovered. The most promising strategy evaluated led to the highly stereoselective formation of a tetrasubstituted cyclobutane via a SmI2-mediated radical reaction − leading to the synthesis of the first exemples of 4-membered carbasugars − then to the formation of the azaspiranic carbon of our target by way of rhodium-catalyzed C-H amination reaction
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Couture, Karine. "Etude de la métallation en série diazinique 1) premier échange iode-lithium avec les alkylamidures de lithium 2) amination électrophile 3) première métallation sans groupe directeur." Rouen, 1995. http://www.theses.fr/1995ROUES020.
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Ce travail consiste en l'étude de la réaction de métallation en série diazinique. Dans une première partie, nous avons pu mettre en évidence pour la première fois en série diazinique, un mécanisme d'halogen-dance avec migration de l'iode. De plus, nous avons pu observer pour la première fois dans cette série, un exceptionnel échange iode-métal avec les alkylamidures de lithium. Cette réaction a été appliquée à la synthèse de leshmaniacides. Dans une seconde partie, nous avons mis au point l'amination électrophile par métallation en série diazinique. Cette réaction d'amination a été appliquée à la synthèse de molécules biologiquement actives et nous a permis d'accéder à un azaanalogue de la Névirapine ainsi qu'à des précurseurs de sulfamides connus. Dans une troisième partie, nous avons tenté d'élargir la gamme des groupes ortho-directeurs en série pyrimidinique (NHCOtBu, CONHtBu). Dans la dernière partie, une nouvelle fonctionnalisation directe des diazines sans groupe ortho-directeur a été réalisée avec succès
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Berman, Ashley M. Johnson Jeffrey Scott. "Catalytic electrophilic amination reactions." Chapel Hill, N.C. : University of North Carolina at Chapel Hill, 2007. http://dc.lib.unc.edu/u?/etd,1086.
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Thesis (Ph. D.)--University of North Carolina at Chapel Hill, 2007.Title from electronic title page (viewed Mar. 27, 2008). "... in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Chemistry." Discipline: Chemistry; Department/School: Chemistry.
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Felten, Anne-Sophie. "Synthèse de N-aminopeptides. Application à la synthèse de nouveaux foldamères." Thesis, Vandoeuvre-les-Nancy, INPL, 2007. http://www.theses.fr/2007INPL095N/document.
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Ce travail décrit la synthèse, l’oligomérisation et l’étude structurale de [alpha-N-amino]mères. En extrapolant une stratégie de synthèse originale d’alpha-hydrazinoacides optiquement purs développée au LCPM nous avons pu obtenir de manière satisfaisante les N-aminodipeptides, précurseurs indispensables à la suite du projet. Nous avons pu montrer que l’activation du partenaire acide impliqué dans la réaction clé de Mitsunobu, habituellement obtenue par l’utilisation du groupement phtalimide, pouvait être avantageusement réalisée par l’introduction d’une fonction hydrazone à caractère fortement électroattracteur. Une extension de cette méthode de synthèse sur résine est un résultat qui constitue une mise en œuvre efficace de la réaction de Mitsunobu en SPS. Les N-aminodipeptides obtenus ont ensuite été engagés dans des réactions d’oligomérisation. Une étude préliminaire en phase liquide a permis de démontrer la faisabilité d’un couplage peptidique classique entre deux unités pseudopeptidiques déprotégées. La suite de l’étude a été effectuée sur phase solide et nous a permis d’obtenir les tous premiers oligomères à squelette alpha-N-aminopeptidique jamais synthétisés à ce jour. Enfin, dans le troisième chapitre, ces oligomères ont été étudiés par modélisation moléculaire et par différentes méthodes spectroscopiques (RMN, IR) qui ont permis de mettre en évidence un repliement par l’établissement de liaisons hydrogène intramoléculairesThis work describes the synthesis, the oligomerization and the structural study of N-aminopeptides. By extrapolating an original strategy of hydrazinoacids synthesis developed in the LCPM we were able to obtain N-aminodipeptides in high optical purity in a satisfactory way. These compounds were the indispensable precursors in order to continue the project. We were able to show that the activation of the acidic partner involved in the key reaction of Mitsunobu usually obtained by the use of the phtalimide group, could be advantageously realized by the introduction of a hydrazone moiety with strong electron-withdrawing character. An extension of this method on solid support is a result which constitutes an effective application of a Mitsunobu protocol in Solid Phase Organic Chemistry. The Naminodipeptides thus obtained were studied in reactions of oligomérisation. A preliminary study in liquid phase allowed to demonstrate that a classic peptidic coupling reaction could occur between two pseudopeptidic units. The continuation of the study was made on solid phase and allowed us to obtain the first [alpha-N-amino]peptides never synthesized to this day. Finally, in the third chapter, these oligomers were studied by molecular modelling and various spectroscopic methods (NMR, IR) who allowed to suggest a folding by the establishment of intramolecular hydrogen bonds
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Nicolas, Mathieu. "Synthèse de copolymères ioniques réactifs pour la fonctionnalisation de nanocellulose : application au développement de membranes échangeuses d’ions." Thesis, Lyon, 2021. https://tel.archives-ouvertes.fr/tel-03789605.
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Les membranes échangeuses d’ions (ou membranes électrolytes) actuellement utilisées au sein des dispositifs de stockage électrochimique (batteries et piles à combustibles) sont généralement issues d’une synthèse polluante, complexe et coûteuse. L’archétype le plus étudié est un ionomère perfluorosulfoné connu sous le nom de Nafion, qui remplit les prérequis d’une membrane ionique performante : haute résistance mécanique et thermochimique, conduction ionique élevée et faible gonflement. La nanocellulose est un matériau polymère biosourcé pouvant être utilisé pour la production de membranes appelées nanopapiers et possédant une excellente résistance mécanique. Cependant, ces matériaux doivent être modifiés chimiquement pour remplir le rôle d’une membrane électrolyte. L’objectif de cette thèse est donc de synthétiser de nouvelles membranes électrolytes à partir du greffage de copolyélectrolytes réactifs sur la surface de nanocelluloses. Cette étape de greffage « onto » repose sur la présence de fonctions amines primaires réactives au sein du copolyélectrolyte. Celles-ci pourront réagir par amination réductrice avec des fonctions aldéhydes localisées sur la surface des nanocelluloses et préalablement introduites par une étape d’oxydation au périodate de sodium (NaIO4). Dans une première partie, la copolymérisation radicalaire a été utilisée pour synthétiser ces polyélectrolytes réactifs suivant deux approches distinctes. La première approche a consisté à modifier un précopolymère poly(styrène sulfonate)-co-poly(acrylamide) (PSS-PAA) par la réaction de Hofmann pour former un poly(styrène sulfonate)-co-poly(vinylamine) (PSS-PVAm) contenant entre 6 et 58% de fonctions amines. La seconde approche a été basée sur la modification chimique d’un copolymère poly(styrène sulfonate)-co-poly(chlorométhyl styrène) (PSS-PCMS) par une diamine via une substitution nucléophile, afin d’obtenir le dérivé aminé poly(styrène sulfonate)-co-poly(benzylamine) (PSS-PBA). Dans un deuxième temps, le greffage de polyamines commerciales et des copolyélectrolytes synthétisés par amination réductrice sur des nanocelluloses oxydées a été étudié. En particulier, il a été montré que la quantité de polyamine commerciale greffée sur la nanocellulose pouvait être simplement ajustée avec les principaux paramètres expérimentaux, atteignant ainsi une IEC de 4,5 meq/g. Le greffage des copolyélectrolytes synthétisés était cependant limité par des problématiques de solubilisation de fragments cellulosiques. Dans une troisième partie, une première preuve de concept de membrane électrolyte associant nanocellulose et polyamine commerciale par amination réductrice a été mise en évidence. L’étude de l’influence de sa composition sur la conductivité ionique et les propriétés mécaniques ont montré une augmentation de la conductivité jusqu’à 1,1 mS/cm pour les membranes les plus riches en polyamines (3,1 meq/g), la contrainte à la rupture maximale (4,0 MPa) ayant été mesurée pour une valeur d’IEC intermédiaire de 1,6 meq/gIon exchange membranes (or electrolyte membranes) currently used in electrochemical storage devices (batteries and fuel cells) are generally the result of a polluting, complex and expensive synthesis. The most studied architecture is a perfluorosulfonated ionomer known as Nafion, which fulfills almost all the prerequisites of a high-performance ion membrane: high mechanical and thermochemical resistance, high ionic conduction and low swelling. Nanocellulose is a biosourced polymer material that can be used for the production of membranes, also called nanopapers with excellent mechanical strength. However, these materials must be chemically modified to fulfill the role of a polymer electrolyte membrane. The objective of this thesis is therefore to synthesize new electrolyte membranes from the surface grafting of reactive copolyélectrolytes to nanocelluloses. This “grafting onto” technique is based on the presence of reactive primary amine functions within the copolyélectrolyte. These may react by reductive amination with aldehyde functions located on the surface of nanocelluloses and previously introduced by a sodium periodate (NaIO4) oxidation step. In the first place, radical copolymerization was used to synthesize these reactive polyelectrolytes following two distinct approaches. The first approach consisted in modifying a poly(styrene sulfonate)-co-poly(acrylamide) precopolymer (PSS-PAA) by the Hofmann reaction to form a poly(styrene sulfonate)-co-poly(vinylamine) (PSS-PVAm) containing between 6 and 58% of amine functions. The second approach was based on the chemical modification of a poly(styrene sulfonate)-co-poly(chloromethyl styrene) copolymer (PSS-PCMS) by a diamine via nucleophilic substitution to obtain the amino derivative poly(styrene sulfonate)-co-poly(benzylamine) (PSS-PBA). In a second part, the grafting of commercial polyamines and synthetized copolyelectrolytes onto oxidized nanocelluloses by reductive amination was studied. In particular, it was shown that the amount of grafted commercial polyamine could be simply adjusted with the main experimental parameters, reaching an IEC of 4.5 meq/g. However, the grafting of the synthesized copolyelectrolytes was limited by issues of solubilization of cellulosic fragments. The study of the influence of the membrane composition on ionic conductivity and mechanical properties showed an increase in conductivity up to 1.1 mS/cm (3.1 meq/g), while the maximum tensile strength (4.0 MPa) was measured for an intermediate IEC value of 1.6 meq/g
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Allouch, Fatima. "Synthèse et applications de nouveaux complexes métallocéniques multidentes." Thesis, Dijon, 2013. http://www.theses.fr/2013DIJOS002.
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Ce mémoire porte sur l’accès simple et peu coûteux à de nouveaux ligands ferrocéniques aminés et aminophosphinés et leur coordination avec des métaux de transition pour des applications en catalyse homogène.Des métallo-ligands aminés flexibles ont été obtenus et caractérisés après amination réductrice du 1,1’-diformylferrocène. D’autres ligands (N,N) rigides ont été isolés au départ du précurseur du 1,1’-di-tert-butyl-3,3’-diformylferrocène. Des aza-ferrocénophanes ont également été facilement préparés avec ces deux précurseurs carbonylés. Lors de la coordination de ces ligands avec le palladium, un palladacycle original a été isolé et caractérisé par diffraction de rayons X.Des ligands ferrocéniques (N,P) ont été obtenus par trois méthodes: i) ortholithiation de ligands ferrocéniques aminés suivie d’un ajout de chlorophosphine, ii) amination réductrice des ferrocènes formylés substitués ou non en présence d’amine portant une fonction phosphine, iii) substitution directe du ferrocène dilithié par des chlorophosphines comportant un hétérocycle azoté. Leur coordination avec du palladium et du platine a été étudiée. Ces métallo-ligands hybrides ont été impliqués dans des réactions de chlorures d’aryle avec des acides arylboroniques (couplage de Suzuki), ainsi que dans la réaction de Sonogashira avec le couplage de bromures et de chlorures d’aryle avec le phénylacétylèneThis thesis focuses on simple and inexpensive access to new amino and aminophosphine ferrocenyl ligands and their coordination with transition metals for applications in homogeneous catalysis.Flexible amine metallo-ligands were obtained and characterized after reductive amination of 1,1'-diformylferrocene. Other rigid (N,N) ligands were isolated starting from the precursor 1,1'-di-tert-butyl-3, 3'-diformylferrocene. Aza-ferrocenophanes were also easily prepared with these two formyl precursors. During the coordination of these ligands with palladium, a stable and original palladacycle was isolated and characterized by DRX.(N,P) ferrocenyl ligands were obtained by three methods: i) ortholithiation of aminoferrocenyl ligands followed by addition of chlorophosphines, ii) reductive amination of substituted or not formylferrocene in the presence of amine bearing a phosphine function, iii) direct substitution of dilithiated ferrocene by chlorophosphines with a nitrogen-containing heterocycle. Their coordination with palladium and platinum has been studied. These hybrid metallo-ligands have been implicated in the reactions of aryl chlorides to arylboronic acids (Suzuki cross-coupling), as well as in the Sonogashira reaction involving of coupling aryl bromides and chlorides to phenylacetylene
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Tanaka, Yusuke. "Boron-based nonacidic iminium ion generators for amination reactions." 京都大学 (Kyoto University), 2009. http://hdl.handle.net/2433/126494.
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Kyoto University (京都大学)0048
新制・課程博士
博士(工学)
甲第14838号
工博第3135号
新制||工||1469(附属図書館)
27244
UT51-2009-F480
京都大学大学院工学研究科合成・生物化学専攻
(主査)教授 杉野目 道紀, 教授 村上 正浩, 教授 大江 浩一
学位規則第4条第1項該当
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Hensienne, Raphaël. "Nouvelles classes d’iminosucres bicycliques : approche synthétique des squelettes 5-azaspiro[3.4]octane et 6-azabicyclo[3.2.0]heptane." Thesis, Strasbourg, 2016. http://www.theses.fr/2016STRAF049/document.
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Des études antérieures conduites par notre groupe ont permis d’identifier l’α-1-C-nonyl-1,5-didésoxy-1,5-imino-D-xylitol en tant que puissant inhibiteur de la β-glucocérébrosidase – enzyme impliquée dans la maladie de Gaucher. La conformation inhabituelle (chaise inversée) de ce composé nous a incités à étudier plus avant la relation entre conformation et activité biologique des iminosucres. L’objectif de ces travaux de thèse consistait ainsi en la synthèse d’analogues conformationnellement contraints d’iminosucres. Dans un premier temps, trois spiro-iminosucres basés sur un squelette 5-azaspiro[3.4]octane ont été obtenus via une séquence comportant trois étapes clés : formation du cyclobutane par cyclisation radicalaire, introduction de l’azote par C-H amination et formation de la pyrrolidine par métathèse. Dans un second temps, une séquence a été développée pour la synthèse stéréodivergente d’iminosucres bicycliques accolés basés sur un squelette 6-azabicyclo[3.2.0]heptane via l’enchaînement de deux étapes clés : formation de la structure azabicyclique par aldolisation de type Mukaiyama puis oxydation de la cétone résultante en énonePrevious studies performed by our group led to the identification of α-1-C-nonyl-1,5-dideoxy-1,5-imino-D-xylitol as a powerful inhibitor of β-glucocerebrosidase, the enzyme involved in Gaucher disease. This compound’s unusual (inverted chair) conformation prompted us to further study the relationship between iminosugars’ conformation and biological activity. The aim of this PhD work was thus the synthesis of conformationally restricted iminosugar analogues. Firstly, three spiro-iminosugars based on a 5-azaspiro[3.4]octane scaffold were synthesized through a sequence including three key steps: cyclobutane formation by way of radical cyclisation, nitrogen introduction by mean of C-H amination and pyrrolidine formation by way ofmetathesis. Secondly, we developed a sequence dedicated to the stereodivergent synthesis of fused bicyclic iminosugars based on a 6-azabicyclo[3.2.0]heptane scaffold through a succession of two key steps: azabicyclic scaffold formation by mean of Mukaiyama aldol reaction followed by ketone to enone oxidation
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Sapountzis, Ioannis. "New Functionalized Grignard Reagents and their Applications in Amination Reactions." Diss., lmu, 2004. http://nbn-resolving.de/urn:nbn:de:bvb:19-24940.
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Polat, Dilan Emine. "Synthesis of N-Oxyureas and Their Applications in Amination Reactions." Thesis, Université d'Ottawa / University of Ottawa, 2019. http://hdl.handle.net/10393/39839.
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Given the occurrence and diversity of nitrogen-containing molecules, the development of new
amination methods is of significant importance. Indeed, a recent study shows that 60% of the FDA
approved drugs contain a nitrogen heterocycle. Undoubtedly, novel methodologies arising for
uncommon intermediates for the incorporation of nitrogen atoms are needed to access more complex
molecules. The present document focus on the development of new methods for the formation of C-N
and N-N bonds for the synthesis of acyclic and heterocyclic products.
Isocyanates are useful synthons and reactive intermediates. To overcome their toxicity and instability,
blocked (or masked) isocyanates have been developed: an equilibrium generates the isocyanate in-situ,
allowing for safer precursors and better control over the concentration of the reactive isocyanate. This
strategy enables the development of new reactivity, particularly for heteroatom-substituted isocyanates.
However, reactions of oxygen-substituted isocyanates (O-isocyanates) remained severely
underdeveloped. In Chapter 2, bench-stable N-oxy-carbamates and N-oxyureas are reacted under basecatalysis or thermal conditions to form the corresponding O-isocyanate intermediate in situ. In the first
part of this chapter, a survey was performed and optimum experimental conditions for the controlled
formation of O-isocyanate intermediates from the block precursors were found. Gratifyingly, the known
side-reactions of O-isocyanates (trimerization and 1,2-shift) were avoided and different nucleophiles
and substituents were studied for the controlled formation of N-oxyureas via substitution reaction of
blocked O-isocyanates. Cascade reactions provided the opportunity to further develop this controlled
reactivity of O-isocyanates. Herein, the first cascade-reaction of O-isocyanates is portrayed using -
and -aminoester as the partners for the synthesis of hydantoin and dihydrouracil derivatives (>30
examples). Moreover, the conditions were modified to perform the reaction with -alcohol and -
thioesters. Finally, evidence for the O-isocyanate intermediate is provided.
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CAPET, MARC. "Synthese d'amines allyliques : oxydation de sulfones." Paris 6, 1986. http://www.theses.fr/1986PA066547.
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L'amination allylique des olefines est catalysee par le cuivre ; application a la synthese de la gabaculine en 4 etapes. Les regio- et stereoselectivite de cette reaction sont comparees a celles de l'acetoxylation de kharasch et de sosnovsky. Des sulfones sont oxydees par des complexes peroxydique du molybdene en hydroxysulfones a squelette carbone symetrique
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Fumagalli, Fernando. "Química de alcaloides carbazólicos: síntese de Claurailas e de biblioteca de análogos estruturais." Universidade de São Paulo, 2015. http://www.teses.usp.br/teses/disponiveis/60/60138/tde-01072015-095954/.
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Compostos heterociclos estão muito presentes em nossas vidas, desde processos biológicos até em fármacos. Dentre esses compostos, os carbazóis, vem ultimamente se mostrando promissores como alternativa terapêutica para diversas doenças, principalmente para o câncer. Muitos carbazóis são produtos naturais, como é o caso das Claurailas A-D. Baseando-se na estrutura da Clauraila A, esse trabalho propôs o desenvolvimento de uma biblioteca de análogos desse alcaloide a fim de prospecção biológica. Para a síntese da Clauraila A foram estudadas condições ideais da ciclodeidrogenação da diarilamina precursora desse alcaloide, através da reação de Åkermark-Knölker. Para a obtenção dessa diarilamina, foi realizado uma otimização da reação de aminação de Buchwald-Hartwig. Com o processo otimizado, foram obtidos diversos carbazóis, com diferentes padrões de substituição, em rendimentos bons à moderados, entre eles estão os produtos naturais 6-metoximurraianine e Clausenal. O rendimento global obtido na síntese desses produtos naturais e da Clauraila A são semelhantes aos previamente descritos na literatura, no entanto, em nosso trabalho foi realizada a síntese deste alcaloide em número reduzido de etapas. Durante o processo de otimização da reação de Åkermark-Knölker foi demonstrado, pela primeira vez, o uso de acetilacetonato de paládio como fonte de paládio II alternativa ao acetato de paládio. Além disso, com esses resultados foi possível inferir o possível mecanismo dessa reação. Adicionalmente, após tentativas por diversas alternativas sintéticas, foram obtidos compostos dimetilcromenos a partir de aminofenóis utilizando prenal e ácido fenilborônico, que podem ser úteis na síntese de outros carbazóis, como a Clauraila B.Heterocyclic molecules are very important class of compounds in biological processes and drugs designing. Among all of them, carbazoles show great applicability for treatment of several diseases, especially against cancer. Many carbazoles are natural products, and one of our interests is Clauraila A. This work is based on the Clauraila A structure to development of a library of carbazoles for biological applications. The optimal conditions of the Åkermark-Knölker cyclodehydrogenation of diarylamine was studied to obtaind the carbazole core. The diarylamines were obtained by the optimized Buchwald-Hartwig amination reaction. This synthetic strategy was used to obtain the range of carbazoles, with different substituents in good and moderate yields, including natural products 6-methoxymurrayanine and Clausenal. The overall yield obtained in the synthesis of the natural products were similar to those previously described in the literature, however, unlike the literature our synthesis involved a reduced number of steps to obtain the desired product. In the optimization step of Åkermark-Knölker reaction, we first applied palladium (II) acetylacetonate instead of palladium (II) acetate. Moreover, with the achieved results the possible mechanism of this reaction was proposed. Additionally, after several attempts, dimethylchromenos were obtained from aminophenols using prenal and phenylboronic acid, which will be useful in the synthesis of other carbazoles, such as Clauraila B.
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Louillat, Habermeyer Marie-Laure [Verfasser], and Frederic W. [Akademischer Betreuer] Patureau. "Modern dehydrogenative amination reactions / Marie-Laure Louillat Habermeyer. Betreuer: Frederic W. Patureau." Kaiserslautern : Technische Universität Kaiserslautern, 2015. http://d-nb.info/1069104906/34.
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Diamante, Daria. "Transition metal-catalyzed alkoxylation and amination reactions involving propargyl or allyl derivatives." Thesis, Paris 6, 2017. http://www.theses.fr/2017PA066119/document.
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Durant toute ma période de doctorat, passé en co-tutelle entre l'Università degli Studi dell'Insubria et l'UPMC de Paris, j'ai dirigé mes efforts vers l'étude de la formation des liaisons C-O et C-N par de nouvelles réactions catalysées par des métaux de transition.En poursuivant notre projet en cours sur les réactions d'amination et d'alcoxylation catalysées par des métaux de transition intra- et intermoléculaires impliquant la fonctionnalisation C-H, nous avons essayé de réaliser deux procédures d'alcoxylation intramoléculaire de liaisons multiples carbone-carbone pour obtenir des hétérocycles oxygénés et une amination allylique oxydante intermoléculaire pour réaliser des scaffolds azotés.Effectuées au niveau intramoléculaire, les réactions catalysées par des métaux de transition offrent une stratégie polyvalente pour obtenir des molécules cycliques, difficilement obtenues par des méthodes de synthèse conventionnelles et à partir de matériaux de départ facilement disponibles, et représentent l'une des méthodologies clés pour le progrès de la chimie verte et durable.En ce qui concerne les protocoles d'alcoxylation, deux lignées de recherche différentes basées sur la catalyse des métaux de transition appliqués aux réactions de domino ont été étudiées.Les processus domino sont des outils efficaces pour augmenter rapidement la complexité moléculaire par la formation de plus d'une liaison en une seule étape, en respectant la règle de l'économie. Bien que l'approche domino impliquant des alcènes et des allènes soit bien étudiée, des exemples impliquant des alcynes sont quelque peu limités dans la littératureDuring the whole period of my PhD, spent in co-tutorship between Università degli Studi dell’Insubria and UPMC in Paris, I have directed my efforts towards the study of C-O and C-N bonds formation by new transition metal-catalyzed reactions.Pursuing our ongoing project on intra- and intermolecular transition metal-catalyzed amination and alkoxylation reactions involving C-H functionalization, we tried to perform two intramolecular alkoxylation procedures of carbon-carbon multiple bonds to obtain oxygenated heterocycles and one intermolecular oxidative allylic amination to accomplish nitrogen-based scaffolds.Performed at intramolecular level, transition metal-catalyzed reactions offer a versatile strategy to obtain cyclic molecules, not easily obtainable by conventional synthetic methods and starting from readily available starting materials, and represent one of the key methodologies for the progress of green and sustainable chemistry. Dealing with alkoxylation protocols, two different research lines based on transition metal catalysis applied to domino reactions were investigated. Domino processes are efficient tools to rapidly increase the molecular complexity through the formation of more than one bond in a single step, respecting the rule of step economy. While the domino approach involving alkenes and allenes is well investigated, examples involving alkynes are somewhat limited in the literature
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Perez, Arlandis Juan Manuel. "The solvent properties of ionic liquids and their effects on amination reactions." Thesis, Imperial College London, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.440461.
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Ruppel, Joshua V. "Cobalt(II)-Catalyzed Atom/Group Transfer Reactions: Stereoselective Carbene and Nitrene Transfer Reactions." Scholar Commons, 2008. https://scholarcommons.usf.edu/etd/484.
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Metalloporphyrins have been shown to catalyze many fundamental and practically important chemical transformations, some of which represent the first demonstrations of these catalytic processes. The most notable examples include an assortment of atom/group transfer reactions, such as oxene, nitrene, and carbene transfers. Atom/group transfer reactions allow for the direct conversion of abundant and inexpensive alkenes and alkanes into value-added functional molecules. Previous reports from our group have shown that cobalt-porphyrin based carbene and nitrene transfer reactions are some of the most selective and practical catalytic systems developed for cyclopropanation and aziridination. Backed by a family of D2-symmetric chiral cobalt porphyrins our group continues the development of stereoselective carbene and nitrene transfer reactions.
Metal-catalyzed cyclopropanation of olefins with diazo reagents has attracted great research interest because of its fundamental and practical importance. The resulting cyclopropyl units are recurrent motifs in biologically important molecules and can serve as versatile precursors in organic synthesis. Supported by a family of D2-symmetric chiral cobalt porphyrins, we have demonstrated the use of succimidyl diazoacetate as carbene source for a highly diastereo- and enantioselective cyclopropanation process. The resulting cyclopropyl succinimdyl esters are highly reactive and serve as valuable synthons for generating cyclopropylcarboxamides. We have also developed the first cobalt-porphyrin based intramolecular cyclopropanation, which is able to produce the resulting bicyclic lactones in high yields and enantioselectivity.
Nitrene transfer reactions are also an attractive route to produce biologically and synthetically important molecules such as amines and aziridines. Although much progress has been made in nitrene transfer reactions utilizing [N-(p-toluenesulfonyl) imino]phenyliodinane (PhI=NTs) the nitrene source suffers from several drawbacks. Consequently, there has been growing interest in developing catalytic nitrene transfer reactions using alternate nitrene sources. To this end, we have utilized arylsulfonyl azides as nitrene source to explore their use in the development of a cobalt-porphyrin catalyzed enantioselective aziridination system. The cobalt catalyzed process can proceed under mild and neutral conditions in low catalyst loading without the need of other reagents, while generating nitrogen gas as the only byproduct. We have also explored the use of arylsulfonyl azides as nitrene source in a cobalt-catalyzed intramolecular C-H amination process.
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Jin, Rongwei [Verfasser], and Frederic [Akademischer Betreuer] Patureau. "Oxidant Evolution in Metal-Free Redox Amination Reactions / Rongwei Jin ; Betreuer: Frederic Patureau." Kaiserslautern : Technische Universität Kaiserslautern, 2018. http://d-nb.info/1160514399/34.
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Hövelmann, Claas. "Oxidative intramolecular diamination of alkenes with ureas as nitrogen sources : Mechanistic investigations of Pd catalysed and halogen mediated reactions." Université Louis Pasteur (Strasbourg) (1971-2008), 2008. http://www.theses.fr/2008STR13107.
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Morimoto, Masao. "Development of Highly Efficient Synthetic Reactions Catalyzed by Transition Metals." 京都大学 (Kyoto University), 2014. http://hdl.handle.net/2433/188615.
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Pawlikowski, Andrew V. "Developments in late metal-mediated C-N bond forming reactions /." Thesis, Connect to this title online; UW restricted, 2006. http://hdl.handle.net/1773/8489.
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Turnbull, Stanhope. "Study of Bis-Imidazol-2-Ylidines as Ligands for Transition Metal Catalyzed Coupling Reactions." ScholarWorks@UNO, 2004. http://scholarworks.uno.edu/td/214.
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Two bis-imidazol-2-ylidine N-heterocyclic carbenes have been employed as ancillary ligands in an attempt to illustrate their utility in the palladium-mediated preparation of aryl ethers from aryl halides. Ullman-type homo-coupling of the aryl halides persistently occurred instead of ether formation. One of the well known N-heterocyclic carbenes, IPr, was employed with the same results. A variety of reaction conditions and reagents were investigated including solvents, N-heterocyclic carbene species, palladium source, alkoxide base, palladium to ligand ratio and reaction time. Reactivity of the individual N-heterocyclic carbenes as ancillary ligands in the palladium-catalyzed amination reaction of aryl halides was investigated to determine functionality of the carbenes. Alternative procedures to prepare the key intermediates in the synthesis of the bisimidazol- 2-ylidines were developed. In this study the aryl imidazoles were prepared from the corresponding phenol and carbonyldiimidazole. Subsequent N-alkylation then furnished the Nheterocyclic carbenes in high yield. Novel unsymmetrical N-heterocyclic carbenes with aryl and benzylic side groups have been synthesized as models for the subsequent synthesis of unsymmetrical polymer-bound Nheterocyclic carbenes. The unsymmetrical ligands were employed in the palladium-catalyzed amination of aryl halides and in the Suzuki-Miyaura Reaction. Two Merrifield resin polymerbound N-heterocyclic carbene ligands were then synthesized and employed in the aryl amination and Suzuki-Miyaura Reactions. Both reactions were greatly accelerated by the implementation of microwave heating. The Merrifield resin polymer-bound palladium-ligand complexes have been recycled through several reactions without loss of activity.
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Mori-Quiroz, Luis Martin. "Transition metal catalyzed Carbon-nitrogen bond forming reactions." Revista de Química, 2015. http://repositorio.pucp.edu.pe/index/handle/123456789/101381.
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Las reacciones de formación de enlaces carbono-nitrógeno (C–N) son transformaciones fundamentales en la naturaleza y también procesos básicos para la preparación de moléculas y materiales relevantes a las actividades humanas. El desarrollo de reacciones nuevas y eficientes para la formación de enlaces C–N es, por lo tanto, de gran interés en los ámbitos académico e industrial. El progreso logrado en los últimos 20 años se ha enfocado, principalmente, en procesos de formación de enlaces Csp2–N; sin embargo, hay una creciente gama de reacciones catalizadas por metales de transición que permite la introducción de nitrógeno en estructuras alquílicas (formación de enlaces Csp3–N). Este artículo describe una selección de métodos catalíticos modernos para la formación de enlaces C–N.Carbon-nitrogen (C–N) bond forming reactions are fundamental transformations in nature and also basic processes for the preparation of molecules and materials relevant to human activities. The development of new and efficient reactions for the formation of C–N bonds are therefore of great interest in academic and industrial settings. Progress in the last 20 years has focused mainly in Csp2–N bond forming processes; however, there is growing range of transition metal catalyzed reactions for the introduction of nitrogen in alkyl frameworks (Csp3–N bond formation). This article describes a selection of modern catalytic methods for the formation of C–N bonds.
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Aoki, Yuma. "Development of Iron-Catalyzed C-N and C-C Bond Forming Reactions toward Functional Arylamine Synthesis." Kyoto University, 2019. http://hdl.handle.net/2433/242518.
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Manolikakes, Georg. "Transition-Metal Catalyzed Cross-Coupling Reactions of Functionalized Organometallic Reagents, Nickel-Catalyzed Amination of Aryl Chlorides and Preparation and Reactions of Organozinc Reagents." Diss., lmu, 2009. http://nbn-resolving.de/urn:nbn:de:bvb:19-139921.
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Mwenda, Edward. "Beyond asymmetric allylic amination: exploring the chemistry of rhodium-catalyzed reactions of allylic trichloroacetimidates in the synthesis of nitrogen and 1,2-diamine heterocyclic compounds." Diss., University of Iowa, 2018. https://ir.uiowa.edu/etd/6227.
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Chiral amines are ubiquitous functionalities found in the architecture of the natural world and have been embedded into materials, catalysts, pharmaceuticals, agrochemicals, and bioactive natural products. However, limited approaches are accessible for the construction of an enantioenriched tertiary or quaternary-containing amine. This thesis describes the development of new methodologies for the synthesis of 7-membered nitrogen-containing heterocycle and 1,2-diamine compounds.
Chapter one describes the application of dynamic kinetic asymmetric amination (DYKAT) of branched allylic acetimidates in the synthesis of 2-alkyldihydrobenzoazepin-5-ones. These 7-membered-ring aza-ketones are generated in good yield with high enantiomeric excess through sequential rhodium-catalyzed allylic amination with 2-amino aryl aldehydes followed by intramolecular olefin hydroacylation of the resulting alkenals. This two-step procedure is efficient, straightforward and convenient for the enantioselective preparation of these ring systems.
In Chapter two, we further extended the methodology towards the allylic amination of racemic secondary and tertiary allylic trichloroacetimidates possessing β-nitrogen substituents, and proximal nitrogen-containing heterocycles, using the DYKAT transformation to provide branched allylic 1,2-diamines with high enantioselectivity. The catalytic system is versatile in the synthesis of 1,2-diamines possessing two contiguous stereocenters, with excellent diastereoselectivity. Additionally, the nitrogen-containing heterocycles suppress competing vinyl azirdine formation, allowing for the high enantioselective syntheses of 1,2-diamines possessing tertiary and quaternary centers. Chapter three gives a very brief outlook on our efforts in rhodium-catalyzed amination strategy in providing access to a variety of enantiopure α-fluoromethylated allylic amines.
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Wang, Shengdong. "Transition metal-catalyzed reduction reactions adding value to bio-sourced compounds." Thesis, Rennes 1, 2018. http://www.theses.fr/2018REN1S134.
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Le travail de recherche concerne l'utilisation de catalyseurs à base de métaux de transition: ruthénium, iridium, cobalt, argent, pour la transformation de substrats bio-sourcés renouvelables en produits à valeur ajoutée pour l'industrie chimique et l'énergie. La transformation par transfert d'hydrogène de l'acide lévulinique en γ-valérolactone a d'abord été développée avec de nouveaux catalyseurs du ruthénium et de l'iridium porteurs d'un ligand dipyridylamine et d'un chlorure en utilisant l'acide formique comme source d'hydrogène. Puis de nouveaux catalyseurs zwitterioniques de type ruthénium et iridium(sulfato)(dipyridylamine) ont été préparés et ils ont conduit aux meilleures productivités observées pour la réduction de l'acide lévulinique en γ-valérolactone par hydrogénation directe. Sur la base des excellentes performances des complexes iridium(sulfato)dans des processus de réduction, l'amination réductrice de l'acide lévulinique et de l'acide o-formylbenzoïque a été réalisée et a permis la synthèse efficace de dérivés de type pyrrolidones, en particulier à partir d'amines primaires encombrées. La déshydrogénation sélective de l'acide formique dans des conditions douces sans additif en milieu aqueux ou en absence de solvant a été développée avec les mêmes types de catalyseurs de l'iridium porteurs du ligand modifié diméthylaminodipyridylamine. Finalement, une méthode d'hydrogénation douce de cétones a été mise en évidence en présence d'un système catalytique à base de nanoparticules d'argent générées in situ. Ce système catalytique permet d'obtenir de bonnes efficacité et sélectivité vis-à-vis d'autre groupement fonctionnelsThis research work deals with the use of catalysts based on transition metals, such as ruthenium, iridium, cobalt, silver for transformations of renewable bio-based substrates to valuable products for applications in chemical industry and energy. The transfer hydrogenation of levulinic acid to γ-valerolactone with novel ruthenium- and iridium(dipyridylamine)chloride complexes using formic acid as hydrogen source was first developed. Then, novel zwitterionic ruthenium and iridium(sulfato)(dipyridylamine) catalysts were prepared, which displayed the highest turnover numbers reported for the reduction of levulinic acid into γ valerolactone using H₂ as hydrogen source. Based on the high catalytic performance of the iridium(sulfato)complexes in reduction processes, the efficient reductive amination of levulinic acid and o formylbenzoic acid, in particular with bulky primary amines, for the synthesis of pyrrolidone derivatives was disclosed. The selective dehydrogenation of formic acid under mild conditions in aqueous media or neat conditions without using an organic additive has been developed using iridium catalysts of the same family equipped with a modified dimethylaminodipyridylamineas ligand. Finally, an unprecedented hydrogenation of ketones in the presence of in situ generated silvernanoparticleswas discovered. High efficacy and functional group selectivity have been achieved in most cases
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Check, Christopher. "Palladium-Catalyzed Inter- and Intramolecular Allylic Oxidation Reactions of Olefins." The Ohio State University, 2012. http://rave.ohiolink.edu/etdc/view?acc_num=osu1348618169.
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Anderson, Mattias. "Amine Transaminases in Multi-Step One-Pot Reactions." Doctoral thesis, KTH, Industriell bioteknologi, 2017. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-199646.
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Amine transaminases are enzymes that catalyze the mild and selective formation of primary amines, which are useful building blocks for biologically active compounds and natural products. In order to make the production of these kinds of compounds more efficient from both a practical and an environmental point of view, amine transaminases were incorporated into multi-step one-pot reactions. With this kind of methodology there is no need for isolation of intermediates, and thus unnecessary work-up steps can be omitted and formation of waste is prevented. Amine transaminases were successfully combined with other enzymes for multi-step synthesis of valuable products: With ketoreductases all four diastereomers of a 1,3-amino alcohol could be obtained, and the use of a lipase allowed for the synthesis of natural products in the form of capsaicinoids. Amine transaminases were also successfully combined with metal catalysts based on palladium or copper. This methodology allowed for the amination of alcohols and the synthesis of chiral amines such as the pharmaceutical compound Rivastigmine. These examples show that the use of amine transaminases in multi-step one-pot reactions is possible, and hopefully this concept can be further developed and applied to make industrial processes more sustainable and efficient in the future.QC 20170113
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Wu, Fan. "Iodide-Catalyzed Alkene Oxyamination Reactions for the Synthesis of Nitrogen-Containing Heterocycles." University of Toledo / OhioLINK, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=toledo1576248441561743.
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Liang, Shengwen. "Nitrene Transfer Reactions Mediated by Transition Metal Scorpionate Complexes." Ohio University / OhioLINK, 2012. http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1339005115.
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Igdir, A. Cigdem. "Reinvestigation Of The Synthetic And Mechanistic Aspects Of Manganese(iii) Acetate Mediated Reactions Synthesis Of 1,2,4-trisubstituted Pyrroles Via Amination / Annulation Reactions Of Chloroenones With Chiral Amine Compounds." Phd thesis, METU, 2006. http://etd.lib.metu.edu.tr/upload/12607643/index.pdf.
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The first part of the thesis presents the reinvestigation of the synthetic and mechanistic aspects of manganese (III) acetate mediated reactions. The main concern about this subject was to perform a ¢- acetoxylation reactions of enones and saturated systems in shorter reactions times and higher yields than the ones known in literature reproducibly. Although successful a ¢
-acetoxylation of a great variety of substrates have been reported so far, there are some problems associated with the use of Mn(OAc)3. Considering that there are not many simple methods for the direct acetoxylation of enones, optimization of Mn(OAc)3 mediated a ¢
-acetoxylation of enones and reaching its maximum potential has a great importance from a synthetic and economical point of view. In the second part of the thesis, 1,2,4-trisubstituted pyrrole derivatives were the target molecules to be synthesized. Although there are quite a number of methods available for the synthesis of pyrroles, most of them involve multistep synthetic operations which lower the overall yield. There are limited reports on the preparation of the enantiomers of pyrrole derivatives having 1-N directly linked to the stereogenic center. Thus, developing a new synthetic method for the efficient preparation of polysubstituted pyrroles without racemization still remains an attractive goal.
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Manolikakes, Georg Verfasser], and Paul [Akademischer Betreuer] [Knochel. "Transition-Metal Catalyzed Cross-Coupling Reactions of Functionalized Organometallic Reagents, Nickel-Catalyzed Amination of Aryl Chlorides and Preparation and Reactions of Organozinc Reagents / Georg Manolikakes. Betreuer: Paul Knochel." München : Universitätsbibliothek der Ludwig-Maximilians-Universität, 2009. http://d-nb.info/1019930152/34.
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Bischoff, Laurent. "Amination electrophile nouveaux reactifs d'amination electrophile. Preparation d'alpha-hydrazino-beta-hydroxyesters. Application a la synthese de molecules d'interet biologique." Paris 6, 1994. http://www.theses.fr/1994PA066495.
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Dans le cadre de l'etude de l'amination electrophile, de nouveaux reactifs d'amination ont ete developpes. Ces reactifs derivant de l'hydroxylamine permettent l'introduction d'une fonction amine n-protegee, a partir d'organolithiens et cuivreux facilement accessibles. Nous avons d'abord elargi l'utilisation du n-tosyloxycarbamate de tertiobutyle metalle developpe au laboratoire, en l'appliquant a l'amination de divers organometalliques: alkyllithiens, alkylcuivreux, boranes et organocuivreux aromatiques obtenus par echange halogene-metal. Nous avons egalement mis au point de nouveaux reactifs d'amination, en modifiant le groupe partant et le groupe protecteur portes par l'azote. Il est ressorti de cette etude que la o-mesitylenesulfonyl-n-allyloxycarbonylhydroxylamine ou msah est un agent d'amination particulierement stable et efficace, permettant pour la premiere fois le transfert du groupe nhalloc sur un organometallique et sur la n-methyl-aniline. Dans une deuxieme partie de ce travail, nous avons synthetise des alpha-hydrazino-beta-hydroxyesters optiquement purs par amination electrophile. Nous avons pu, par l'utilisation d'enolates de dioxanones et de dianions zinciques, ameliorer considerablement la diastereoselectivite de la reaction. De plus, nous avons prepare une serie de beta-hydroxyesters par hydrogenation asymetrique en presence de catalyseurs chiraux au ruthenium. Les exces enantiomeriques obtenus sont de 30 a 99%. Ainsi, la sequence hydrogenation asymetrique amination electrophile diastereoselective nous a permis de synthetiser une large gamme d'alpha-hydrazino-beta-hydroxyesters anti optiquement purs. Nous avons illustre cette methodologie par la synthese des deux enantiomeres anti de la (3)-carboxy-(4)-hydroxy-2,3,4,5-tetrahydropyridazine, un constituant de la luzopeptine a, antibiotique antitumoral. Cette synthese a ete realisee en 7 etapes avec un rendement global de 19% a partir de l'acide 3-(e)-hexenoique commercial. D'autre part, dans des travaux figurant en annexe, des essais d'hydroxylation electrophile de beta-hydroxyesters et de dioxanones ont ete realises, mais les resultats obtenus sont mediocres
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Corona, Prieto Teresa. "Understanding C-H oxidation and amination reactions performed by late first-row transition metals: trapping high-valent metal-O/N species." Doctoral thesis, Universitat de Girona, 2017. http://hdl.handle.net/10803/401684.
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The transformation of C-H bonds into C-O/N bonds is a process of interest in organic synthesis, but controlling the reactivity and selectivity among the multiple C-H bonds existing in most molecules is a challenging task. Traditional methodologies usually rely on the use of stoichiometric reagents that generate important amounts of toxic waste and relatively harsh reaction conditions are required. An alternative to these traditional methods is the use of catalysts, which enable the performance of these transformations under mild conditions, with improved selectivities and using less hazardous reagents. However, finding good catalysts inevitably means that intimate details about the reaction mechanism need to be unraveled. One key issue to further develop more effective catalysts is to understand the mechanism. Thus, this doctoral dissertation is focused on obtaining mechanistic insight into these transformations by trapping the active species that is the high-valent metal-oxygen/nitrogen species based on late first-row transition metalsLa transformació d'enllaços C-H en enllaços C-N/O és un procés interessant en síntesi orgànica, però encara és un repte controlar la reactivitat i selectivitat entre els diferents enllaços C-H presents en les molècules. Les metodologies tradicionals solen estar basades en l'ús de reactius en quantitats estequiomètriques, generant importants quantitats de residus tòxics, i en condicions de reacció agressives. Una alternativa és l'ús de catalitzadors, els quals permeten dur a terme aquestes transformacions en condicions de reacció més suaus, millorant les selectivitats, i utilitzant reactius menys perillosos. No obstant, trobar nous catalitzadors implica conèixer en detall el mecanisme de les reaccions. Per això, aquesta tesi té com a objectiu estudiar els mecanismes d’aquestes transformacions a través de la detecció i estudi de les espècies actives, corresponents a compostos metall-oxigen o metall-nitrogen en alt estat d’oxidació basats en metalls de la primera sèrie de transició
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Liu, Xinyuan. "Gold (I) and platinum (II)-catalyzed hydroamination of alkenes and alkynes and related tandem reactions for synthesis of nitrogen-containing multi-cyclic ring compounds and chiral amines." Click to view the E-thesis via HKUTO, 2010. http://sunzi.lib.hku.hk/hkuto/record/B43911237.
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Liu, Xinyuan, and 刘心元. "Gold (I) and platinum (II)-catalyzed hydroamination of alkenes and alkynes and related tandem reactions for synthesis of nitrogen-containing multi-cyclic ring compounds and chiral amines." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2010. http://hub.hku.hk/bib/B43911237.
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Lizardi, Christopher Lee. "Aldehydic C-H Amination Reactions via Co(II)-Based Metalloradical Catalysis and Construction of Novel Chiral meso-Amidoporphyrin Ligands." Scholar Commons, 2015. https://scholarcommons.usf.edu/etd/5526.
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Medium-sized organic ring synthesis poses a seemingly insurmountable challenge, and because of this it is a field under immense investigation. Heterocyclic containing medium-sized rings are common structural motifs in nature, which has caused researchers to investigate their potential biological activity and properties as materials. This research focused on the grand challenge of medium-sized heterocyclic ring synthesis, providing the synthesis community with new tools to generate these highly evasive products, while elucidating energetic and geometric properties of one of Nature's least understood organic ring systems.
Cobalt(II)-Amidoporphyrins, [Co(D2-Por)], are an emerging class of metalloradical catalysts (MRC) which can facilitate a wide range of atom and group transfer reactions. A strategy was employed using [Co(D2-Por)] to carry out an intramolecular C-H amination reaction using sulfamoyl azides as the radical nitrene source to aminate the highly reactive aldehydic C-H bond. This newfound reaction allowed for the generation of previously unobtainable medium-sized heterocycles, which surprisingly provided a racemic mixture of chiral medium-sized rings.
A wide array of chiral amidoporphyrins including meso-heteroatom containing porphyrins were synthesized as well during the course of research to probe their potential as new chiral ligands for the emerging field of cobalt(II)-amidoporphyrin catalyzed MRC system. A practical synthetic scheme was discovered employing the highly selective Zn(II)-bromoporphyrin synthon to generate a new library of chiral amidoporphyrin ligands for the MRC system through well-established cross-coupling methodologies.
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Fernandez, Sarah [Verfasser], and Paul [Akademischer Betreuer] Knochel. "Chromium- and cobalt-catalyzed cross-coupling and amination reactions and synthesis and reactivity of Pyrido[3,2-f][1,7]naphthyridines / Sarah Fernandez. Betreuer: Paul Knochel." München : Universitätsbibliothek der Ludwig-Maximilians-Universität, 2016. http://d-nb.info/1104128934/34.
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Fields, Kimberly Bliss. "The Design and Synthesis of Functionalized Porphyrins and Their Applications in Group Transfer Reactions, Medicine, and Materials." Scholar Commons, 2010. http://scholarcommons.usf.edu/etd/3461.
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Porphyrins and their analogs are a class of chemically and biologically important compounds that have found a variety of applications in different fields such as catalysis, medicine, and materials. The physical, chemical, and biological dependence of the peripheral substituents of porphyrins on their properties has prompted great effort towards the synthesis of new porphyrins with different electronic, steric, and conformational environments. To this end, porphyrins have been prepared using a modular approach from bromo- and triflate synthons. These synthons underwent palladium-catalyzed cross-coupling with chiral amines, amides, alcohols, and boronic esters to create products that were tested for biological activity.
Metalloporphyrins were screened as catalysts for cyclopropanation and C-H amination, yielding excellent results. By changing the porphyrin catalysts’ chiral groups, all four enantiomers could be produced in the cyclopropanation of styrene derivatives with ethyl diazoacetate (or t-butyl diazoacetate). Similarly, a variety of sultams were produced from benzenesulfonyl azides in high yields and high enantioselectivities using chiral cobalt porphyrins as catalysts.
Porphyrins, metalloporphyrins, and the catalytic products generated were tested for activity in a variety of medicinal collaborations, namely as therapeutics for methicillin-resistant Staphylococcus aureus, Alzheimer’s disease, malaria, viral infections that include influenza and herpes, and cancer, as well as biological studies with ferrochelatase. They were also used in materials experiments with two different polymer groups.
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Denis, Alexis. "Fonctionnalisations selectives a l'aide des complexes du palladium : synthese de composes d'interet biologiques, cyclopropanes vinyliques, aryl-3 oxazolidinones-2 (inhibiteurs potentiels de la monoamine oxydase)." Paris 6, 1987. http://www.theses.fr/1987PA066335.
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Ce travail porte sur l'utilisation du palladium (o) pour la synthese de molecules d'interet biologique. En premier lieu, on decrit la synthese stereoselective de cyclopropanes vinyliques et de pyrethrinoides. Dans un second temps, on etudie l'echange acetate phenol et l'amination de derives allyliques fibonctionnels. Enfin, on presente la synthese d'aryl-3 dihydroxy-5,5 oxazolidones-2 erythro et threo et etudie leur utilisation en tant qu'inhibiteur d'enzyme monoamine oxidase