Dissertations / Theses on the topic 'One-pot catalysis'
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1
Boscaro, Paolo. "One-pot synthesis of structurated of TiO2 materials easy to handle (not nanoparticles) for photocatalysis under visible light and sunlight." Thesis, Montpellier, Ecole nationale supérieure de chimie, 2016. http://www.theses.fr/2016ENCM0009.
Abstract:
L’objectif de ce travail est de développer des matériaux à base de titane sous la forme de monolithe capable d’assurer des réactions photo catalytiques en flux, sous la lumière du soleil ou la lumière visible. Ces matériaux doivent présenter des propriétés physiques et chimiques particulières afin de pallier aux inconvénients des photocatalyseurs classiques qui limitent leur efficacité, à savoir : la stabilité mécanique, la perte de charge, le faible transport de masse, et le controle du temps de contact, la gamme de longueur d’onde d’absorption réduite, le temps de vie de la charge photo-générée. Trois voies de synthèse de monolithes TiO2 ont ainsi été élaborées et optimisées pour atteindre la forme et la dimension adéquate à l’application visée. Les monolithes TiO2 présentant une porosité bimodale macro-mésoporeux interconnectée, avec une stabilité mécanique et chimique élevée, ont été utilisés comme un microréacteur photocatalytique sous flux sous différentes conditions de flux. Les monolithes synthétisés ont montré une absorption plus élevée dans la lumière du visible, ce qui leur permet d’être efficaces dans une plus grande gamme de rayonnements. L’absorption dans le visible des monolithes de TiO2 est attribuée aux espèces carbonées et/ou azotées contenues dans le matériau. Ces matériaux on été testes dans la dégradation de l’orange G en milieu aqueux. Ce suivi a été réalisé à la fois en réacteur en batch et en flux, à la lumière du soleil, sous lumière du visible et sous lumière UV. Tous les tests catalytiques ont conduit à une dégradation totale du polluant avec une cinétique plus rapide que pour le matériau de référence (TiO2 P25) sous rayonnement visible. De plus aucune désactivation n’est détectée après 85 h sous circulation de la solution dans les conditions du flux opératoire. L’autre utilisation envisagée pour ces monolithes est le water-splitting (dissociation de l’eau en hydrogène et oxygène). Pour cela des films autoportés (~ 1 mm d’épaisseur) de compositions similaires aux précédents matériaux ont été synthétisés afin de permettre une activité photo-catalytique de dissociation de l’eau sous lumière visible. Afin d’augmenter la production d’hydrogène, des matériaux associant une couche d’oxyde de cuivre et une couche de TiO2 ont été réalisés par l’optimisation de la méthode précédenteThe aim of this study is to develop titania based materials able to perform photocatalytic reaction in flow condition, under sunlight or visible light, with special physical and chemical properties in order to overcome common photocatalysts’ deficiencies like: mechanical stability, pressure drop, low mass transfer and contact time, reduced wavelength range absorption, photo-generated charge lifetime, and in general all features that limit photocatalysts efficiencies. Three synthesis methods have been developed and optimized to obtain TiO2 monoliths with shape and dimension that can be adapted to any specific application. TiO2 monoliths, displaying bimodal macro-mesoporous interconnected network together with an elevated mechanical and chemical stability, have been used as flow photocatalyst microreactor under different flow rate conditions. Synthesized monoliths displayed enhanced visible light absorption, enabling them to efficiently operate in a vast range of illumination. TiO2 monoliths absorption on the visible range of the spectrum is attributed to carbon-nitrogen containing species within the material. Orange G degradation in aqueous medium have been performed both in batch and flow reactors under sunlight, visible light and UV light. All reactions resulted in complete mineralization of pollutant, with higher degradation rate than TiO2 nanoparticles benchmark material (P-25) when visible light is used. No photocatalyst deactivation have been detected after 85 hours of wastewater treatment in flow conditions. Similar TiO2 material, with a free-standing thick-film shape, have been used to perform photocatalytic water splitting under visible light. Another strategy has been developed to synthesize a TiO2/CuO self-standing film to enhance charge separation giving unexpected results in terms of hydrogen production
2
Giorgi, Pascal. "Nouvelles réactions à économie d'atomes et d'étapes basées sur la catalyse par des nanoparticules d'or et la multicatalyse. Applications dans la synthèse de chimie fine et des odorants." Thesis, Université Côte d'Azur (ComUE), 2017. http://www.theses.fr/2017AZUR4127.
Abstract:
L'élaboration de méthodes de synthèse, basées sur l’utilisation d’espèces métalliques a été un sujet de tous les instances en chimie organique. Malgré l’efficacité des métaux utilisés en catalyse homogènes, leurs procédures de recyclage restent limitées. Ce pourquoi, une contrainte supplémentaire a été placée dans la conception de catalyseurs, pouvant offrir à la fois l'efficacité de la catalyse homogène et le recyclage de l’hétérogène. Dans ce contexte, les nanoparticules métalliques sont apparues comme objet phare, en raison de leurs propriétés physico-chimiques inégalées. On a découvert que les nanoparticules de métaux nobles présentaient des propriétés catalytiques similaires dans certains cas, aux complexes monoatomiques. De plus, les Au NPs ont montré une activité catalytique remarquable dans l'oxydation d’alcools activés sous O2. Nous avons donc envisagé des procédures multicatalytiques, basées sur les NPs d’Au. Notre choix d'utiliser des catalyseurs solides était pertinent, puisque les nano-catalyseurs, pour lesquels la fraction de sites actifs se trouve en surface, limitent les risques de cross-quenching. Ici, nous présentons trois nouveaux procédés bicatalytiques permettant l’accès, à des chromenes/quinoléines (53-93%) via une oxydation / Michael Addition/ aldolisation, combinant nanocatalyse et catalyse basique, l’accès à des ortho-THC (50-81%) via oxydation / arylation / cyclisation, combinant nanocatalyse et catalyse supportée, ainsi qu’une une oxydation / hydrolyse en cascade, pour accéder à l’HMLA (86%, sel 93%), un grand panel de produits d'activité biologique reconnue, utilisé en parfumerie ou visant une pré-industrialisation via la chimie en flux continuElaboration of synthetic methods based on metal-catalyzed reactions has been a hot topic in organic chemistry. Despite good efficiency, catalysis proceeding homogeneously, are limited in the operation of recovering/recycling of the catalysts. An important stress was placed to design catalysis, offering both the efficiency of homogeneous catalysts and the recyclability of heterogeneous catalysts. In this context, metal nanoparticles merged as a key tool, due to their unique physical and chemical properties. Notably, Au NPs have shown remarkable catalytic activity in the oxidation of activated alcohols under O2 atmosphere. Since now, the access to more complex molecules is the next step forward for this field, we envisioned multicatalytic roads, based on the oxidation of activated alcohols via supported Au NPs. Our choice of using solid catalysts was relevant, since nanostructured catalysts for which the fraction of active sites are located on the surface, limit the risk of cross-quenching. The latter carbonyl formed, could be further converted in situ, via tandem protocol. Herein, we developed novel, atom- and step-economical bicatalytic one-pot processes, to access substituted chromenes/quinolines (53-93%) by tandem oxidation/hetero-Michael addition/aldolisation combining nanocatalysis and base catalysis, ortho-THCs (50-81%) via tandem oxidation/arylation/cyclisation combining nanocatalysis and supported catalysts and a tandem cascade oxidation/hydrolysis to access HMLA (86%, sel 93%). A large panel of products of biological activity relevance, pertaining to the fragrance chemistry or aiming in some cases, pre-industrial scalability via continuous flow applications
3
Kudaibergenov, S. E., G. S. Tatykhanova, and E. Baigaziyeva. "Preparation, Characterization and Catalytic Activity of Gold Nanoparticles Stabilized by Hydrophilic Polymers." Thesis, Sumy State University, 2012. http://essuir.sumdu.edu.ua/handle/123456789/35034.
Abstract:
Optical properties, structure, size and morphology of colloidal gold nanoparticles (AuNPs) stabilized by
a series of hydrophilic polymers possessing nonionic, anionic, cationic and amphoteric nature were characterized by visible spectroscopy, dynamic light scattering (DLS), X-ray diffraction (XRD) and scanning electron microscopy (SEM), transmission electron microscopy (TEM). The polymer-protected AuNPs were prepared by “one-pot” synthetic protocol. The kinetics of formation of AuNPs was determined. The influence of
the molecular weight (Mw) of polymers and concentration of AuNPs on the size of AuNPs was shown. The
catalytic activity of polymer-protected AuNPs with respect to hydrogenation of 4-nitrophenol was studied.
High conversion degree of 4-nitrophenol to 4-aminophenol was evaluated by visible spectroscopy.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35034
4
Lainer, Bruno. "A multicatalytic approach to enantio-, and diastereoselective arylation of alcohols." Electronic Thesis or Diss., Strasbourg, 2023. http://www.theses.fr/2023STRAF080.
Abstract:
Les groupements alcooliques sont présents dans une grande diversité de produits chimiques fins précieux issus de la nature et de la synthèse, c'est pourquoi les méthodes permettant leur diversification structurelle sont recherchées. Cependant, la modification de la structure des alcools à certaines positions non réactives, même avec l'aide de la catalyse, reste un défi ou nécessite des procédures multi-étapes fastidieuses et souvent coûteuses. Récemment, une attention accrue a été accordée à la multicatalyse, qui combine plusieurs catalyseurs au sein d'un même système, ce qui permet de découvrir des réactivités auparavant inaccessibles ou d'accroître l'efficacité globale des transformations en plusieurs étapes. Les méthodes décrites ici permettent l'α- et la β-arylation diastéréo- et énantiosélective d'alcools. En combinant des catalyseurs à base de Ru et de Pd, il est possible de réaliser une β-arylation énantiosélective (et diastéréodivergente dans le cas d'alcools portant déjà des stéréocentres) sans précédent d'alcools primaires. En outre, dans le cadre d'une catalyse relais séquentielle, il est possible d'obtenir des alcools benzyliques secondaires enrichis enantioénergie à partir de divers produits de départ disponibles, tels que des alcools primaires ou des alcools portant une double liaison. Dans l'ensemble, ces protocoles démontrent le potentiel de la multicatalyse en tant qu'outil synthétique pour diversifier les alcools. Dans un contexte plus large, cette thèse ouvre la voie à la conception de nouvelles stratégies et méthodes multicatalytiques pour une synthèse efficaceAlcohol moieties are present in a great diversity of valuable fine chemicals from nature and synthesis, therefore methods enabling their structural diversification are sought after. However, modifying the structure of alcohols at certain unreactive positions, even with the aid of catalysis, remains a challenge or requires tedious often wasteful multistep procedures. Recently, increased attention has been paid to multicatalysis, which combines multiple catalysts within one system, enabling the discovery of previously inaccessible reactivities or increasing the overall efficiency of multistep transformations. Described within are methods which enable the diastereo-, and enantioselective α-, and β-arylation of alcohols. By combining Ru- and Pd-based catalysts the unprecedented, enantioselective (and diastereodivergent in the case of alcohols already bearing stereocenters) β-arylation of primary alcohols can be carried out. Also, under sequential relay catalysis enantioenriched secondary benzylic alcohols can be obtained from a variety of available starting materials, such as primary alcohols, or alcohols bearing a double bond. Overall, these protocols demonstrate the potential of multicatalysis as a synthetic tool for diversifying alcohols. In a broader context, this thesis sets the stage for devising novel, multicatalytic strategies and methods for efficient synthesis
5
Cusati, Giuseppe. "La catalyse hétérogène au palladium en chimie fine : une étude sur la synthèse " one-pot " de stilbènes et bibenzyles : application à la synthèse de styrènes et aryl-indoles." Phd thesis, Université Claude Bernard - Lyon I, 2009. http://tel.archives-ouvertes.fr/tel-00876267.
Abstract:
Les synthèses " one pot " multi-étapes efficaces et éco-compatibles ont été envisagées pour la synthèse de molécules potentiellement bioactives tels que les systèmes bis(bibenzyliques) et leurs précurseurs stilbéniques ou bibenzyliques par catalyse hétérogène au palladium. Une synthèse " one-pot " impliquant une réaction de couplage de Heck suivie d'une hydrogénation des stilbènes ainsi formés a été mise au point en présence de Pd/C. Cette stratégie c'est révélée être limitée lors de l'application à des substrats désactivés et stériquement encombrées. Couplée au manque de disponibilité commerciale d'oléfines aromatiques intéressantes pour nos objectifs, nous avons mis au point une synthèse de styrènes par catalyse hétérogène à partir d'halogénures d'aryles et du vinyltrifluoroborate de potassium impliquant un couplage de Suzuki-Miyaura. Cette vinylation hétérogène a été ensuite appliquée à la synthèse " one-pot " de stilbènes. Des études d'optimisation de ce procédé sont encore en cours. Les stilbènes ainsi obtenus ont été utilisée pour la synthèse de bis(bibenzyles) ouverts et fermés. Pour ce faire différentes stratégies " one-pot " ont été évaluées au cours de ces travaux et des bis(stilbènes) ont été obtenus avec des rendements compris entre 30% et 50%. Les bis(stilbènes) ainsi obtenus ont été l'objet d'études en hydrogénation. A ce jour aucune de nos tentatives n'a permis l'obtention de bis(bibenzyles) quelles que soient les conditions employées. Des études sont en cours pour comprendre les raisons de ces résultats et obtenir les bis(bibenzyles) cibles de nos travaux
6
Luciani, Sara. "Sintesi enantio- e diastereoselettiva di atropoisomeri N-N." Master's thesis, Alma Mater Studiorum - Università di Bologna, 2021. http://amslaurea.unibo.it/24360/.
Abstract:
Gli atropoisomeri rappresentano la principale e più studiata classe di composti aventi chiralità assiale. Nel corso degli anni, gli studi su atropoisomeri C-C e C-X sono aumentati notevolmente, vista anche la possibilità di utilizzarli come leganti chirali per catalizzatori di sintesi asimmetrica. Tuttavia, lavori riguardanti atropoisomeri con asse chirale X-X sono abbastanza rari in letteratura, soprattutto per quanto riguarda la sintesi asimmetrica. Il lavoro che viene presentato è incentrato sullo sviluppo di una metodologia di sintesi asimmetrica per la preparazione di una nuova classe di idrazine atropoisomeriche sul legame N-N. È stata sfruttata una sintesi articolata in due step: una reazione di α-amminazione di carbonili con il di-terz-butil azodicarbossilato via enammina e una reazione di alchilazione con benzil bromuro in condizioni di Phase Transfer Catalysis. I substrati carbonilici testati sono stati l’iso-butirraldeide e la 2-fenil propanaldeide, che portano rispettivamente a una sintesi enantioselettiva e diastereoselettiva. Attraverso degli screening, sono state individuate le condizioni di reazione ottimali di entrambi gli step, sia in termini di resa che di enantio- e diastereoselettività finali. Nel complesso, è stato ottenuto un modesto eccesso enantiomerico nella reazione enantioselettiva e buoni rapporti diastereoisomerici nella reazione diastereoselettiva, che possono essere considerati degli importanti punti di partenza per ulteriori futuri lavori di ottimizzazione del sistema catalitico. In aggiunta, l’intera sintesi diastereoselettiva è stata implementata in una procedura one-pot che evita lo step di purificazione intermedio. Allo scopo, sono state necessarie ulteriori indagini per valutare la compatibilità delle due reazioni nello stesso ambiente di reazione.
7
Chen, Xu. "Investigation of the Phase transformation in FePtM nanoparticles (M= Ag, Cu) at atomic scale for optimized oxygen reduction catalysis." Thesis, Normandie, 2019. http://www.theses.fr/2019NORMC235.
Abstract:
Les piles à combustible à membrane échangeuse de protons sont prometteuses en tant que nouveaux dispositifs de conversion d'énergie en raison de leur rendement élevé et de leur faible impact sur l'environnement. Cependant, les charges de Pt nécessaires pour compenser la mauvaise cinétique de la réaction de réduction de l'oxygène entravent leurs applications à grande échelle. Récemment, il est devenu possible d'améliorer l'activité des catalyseurs en exploitant des effets géométriques et/ou électroniques. Ainsi, les alliages binaires à base de Pt avec une structure ordonnée ont-ils montré une activité et une durabilité améliorées. Ce travail a étudié des nanoparticules FePtAg et FePtCu ordonnées issues de la synthèse « one‒pot ». Dans FePtAg, nous avons démontré que la transformation vers la structure ordonnée était induite par le dopage Ag; une coercivité de 5.23 kOe et des nanoparticules de FePtAg de taille ultrafine (3.5 ± 0.5 nm) ont été obtenues. Pour les nanoparticules de FePtCu, l’effet d’alliage de Cu s'est avéré constituer la force motrice pour la mise en ordre. En comparaison avec le Pt/C de référence, nos nanoparticules de Cu/FePtCu à structure noyau/coquille optimisées présentent une activité massique 4 fois supérieure avec une atténuation en durabilité de seulement 3% contre 34.2%. Enfin, une activité massique supérieure de 11.7 fois à celle de Pt/C a été obtenue pour des nanoparticules de FePtCu avec une structure cœur/coquille Cu/FePt en forme d’octaèdres tronquésProton exchange membrane fuel cells are promising as novel energy conversion devices due to their high efficiency and low environmental impact. However, the platinum loadings needed for compensating the poor kinetics in the oxygen reduction reaction hinder their widespread applications in new energy vehicles and stations. Recently, it has become possible to enhance the catalysts activity based on geometrical and/or electronic effects. In this vein, Pt−based binary alloys with ordered structure have demonstrated enhanced activity and durability, while, contributing to decrease the weight of Pt. In this work, we have investigated ordered FePtAg and FePtCu nanoparticles from one‒pot synthesis, with the objective to develop high performance catalysts by improving their activity and durability. In FePtAg, the phase transition to ordered structure was shown to be induced by Ag doping; a high coercivity of 5.23 kOe and ultrafine size FePtAg nanoparticles (3.5 ± 0.5 nm) has been achieved. For the FePtCu nanoparticles, the Cu alloying effect was found to constitute the driving force for ordering. As related to benchmark Pt/C, our optimized core‒shell structured Cu/FePtCu nanoparticles exhibited a mass activity 4 times higher with only 3 % durability attenuation in contrast to 34.2%. Finally, a mass activity of 11.7 times larger than Pt/C was achieved for optimized FePtCu nanoparticles, with core‒shell Cu/FePt structure and truncated‒octahedron shape
8
Isleyen, Alper. "One-pot Synthesis Of Chloroalcohols And Their Lipase Mediated Kinetic Resolution - Ferrocenyl Aziridinylmethanols As Chiral Ligands In Enantioselective Conjugate Diethylzinc Addition To Enones." Phd thesis, METU, 2007. http://etd.lib.metu.edu.tr/upload/12608857/index.pdf.
Abstract:
An unexpected tricyclic ether formation instead of acetate addition to the double bond of a norbornene derivative aroused our interest to explore the mechanism of this reaction. Mechanistic studies showed that methylene diacetate (MDA) was formed in the stock solution (NBu4OAc + dichloromethane) and decomposed to formaldehyde under Lewis or Brønsted acid conditions. Formaldehyde and olefin condensation (Prins reaction) clearly explains the formation of the unexpected product. Same methodology was then successfully applied to develop a one-step procedure for the synthesis of 3-chloro-3-arylpropanols, which are important starting materials for the synthesis of biologically active benzanilide derivatives. Styrenes were reacted with MDA in the presence of boron trifluoride to give the corresponding 3-chloro-3-arylpropanols in 36&
#8211
84% yield. The second part of the thesis involves kinetic resolution of 3-chloro-3-arylpropanols by lipase mediated acylation which are described for the first time. Acylation with the CCL provided the best enantioselectivity amongst the enzymes used. Enantiomerically enriched products with up to 78% ee were obtained after two successive lipase-mediated acylations. Different substituents on the aromatic ring and bromide, instead of chloride, at the benzylic position of the substrates were found to have no drastic influence on the enantioselectivity of the reaction. In the last part, easily available ferrocenyl substituted aziridinylmethanols (FAM) were complexed with nickel to catalyze the enantioselective diethylzinc addition to various enones with ee&
#8217
s reaching 82%. The ligands can be recovered and used without losing their activity. The sense of asymmetric induction was found to be dependent on the configuration of the aziridine ring.
9
Ellis, Richard D. "Reductive amination catalysed by iridium complexes." Thesis, University of Sussex, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.341064.
10
Lorusso, Patrizia. "Metal catalysed alkylation of carbonyl compounds with formaldehyde." Thesis, University of St Andrews, 2015. http://hdl.handle.net/10023/7823.
Abstract:
Formaldehyde is a chemical used widely in the manufacture of building materials. A remarkable example is represented by the Lucite two-step Alpha technology for the large scale production of methyl methacrylate (MMA), the essential building block of all acrylic-based products. Esters and ketones are important intermediates in the manufacture of acrylate esters therefore α-hydroxymethylenation of carbonyl compounds using formaldehyde as a one carbon alkylating agent and subsequent dehydration to the corresponding methylenated derivatives has been explored in the current work. We report a novel catalytic approach for the synthesis of methyl methacrylate (MMA) via one-pot α-methylenation of methyl propanoate (a chemical intermediate of the ALPHA process) with formaldehyde, generated in situ by Ru-catalysed dehydrogenation of methanol. Elucidation of the mechanism involved in the catalytic dehydrogenation of methanol along with the collateral alcohol decarbonylation reaction was gained through a combined experimental and DFT study. The development of an alternative process where anhydrous formaldehyde is produced in situ would provide a simplification over the current second step of the ALPHA technology where the formaldehyde is initially produced as formalin, subsequently dehydrated to afford anhydrous formaldehyde in order to ensure high selectivity to MMA. As an alternative approach, ketones, in particular 3-pentanone and 2-butanone, were targeted as potential substrates in order to overcome some of the problems related to competing reactions that occur at the ester group. Hydroxymethylenation, followed by dehydration and Baeyer-Villager oxidation, possibly catalysed by enzymes to reverse the normal selectivity, leads to the formation of acrylate esters. The catalytic reaction is enabled by a gold carbene hydroxide complex in such a way that the substrate undergoes C-H activation and the nascent metal alkyl acts as a nucleophile towards the electrophilic formaldehyde, supplied in the form of alcoform* (solution of paraformaldehyde in methanol).
11
Nassar, Hardy Luma. "Tandem reactions using multi-task catalysts." Thesis, Bordeaux 1, 2011. http://www.theses.fr/2011BOR14317/document.
Abstract:
Le développement d’une chimie propre et donc durable est un des challenges majeurs du 21ème siècle dans les pays industrialisés. Étant au cœur de nombreuses découvertes dans divers domaines scientifiques allant de la physique à la médecine, les sciences chimiques doivent jouer un rôle central pour résoudre un certain nombre de problèmes environnementaux auxquels nous devons faire face. Mon travail de thèse s’inscrit dans cette problématique par le développement de méthodologies de synthèse faisant intervenir plusieurs transformations dans le même réacteur. Nous avons notamment développé des séquences réactionnelles appelées HRC (pour Heck-Reduction-Cyclization, en anglais) prenant appui sur le caractère multi-tâche d’un catalyseur à base de palladium. Ces travaux nous ont permis de préparer une grande variété d’hétérocyles ou composés fonctionnalisés parmi lesquels nous pouvons citer les oxindoles, les indanones, ou encore les naphthoxindoles. Ces travaux ont donné lieu pour le moment à quatre publications dans des journaux à comité de lectureThe development of clean chemistry and therefore sustainable is one of the major challenges of the 21st century in industrialized countries. Being in the heart of many discoveries in various scientific fields ranging from physics to medicine, the chemical sciences must play a central role in solving a number of environmental problems we face. My thesis work is part of this problem through the development of synthetic methodologies involving several transformations in the same reactor. We have developed the reaction sequences called HRC (for Heck-Reduction-cyclization) building on the multi-task of a palladium catalyst. This work allowed us to prepare a variety of functionalized heterocycles or compounds from which we can cite the oxindole, the indanones, or the naphthoxindoles. This work has resulted for the time four publications in peer-reviewed journals
12
Zhang, Xiang. "One-pot catalytic reaction of crude glycerin for biopolyols and polyurethane foam production." The Ohio State University, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=osu1306458447.
13
Mostafa, Mohamed A. B. "One-pot transition metal-catalysed processes for the synthesis of biologically active compounds." Thesis, University of Glasgow, 2018. http://theses.gla.ac.uk/8779/.
Abstract:
The first section of this thesis describes the development of a one-pot Pd(II)- catalysed Overman rearrangement, Ru(II)-catalysed ring closing enyne metathesis reaction and a hydrogen bond-directed Diels-Alder reaction for the diastereoselective synthesis of C-5 substituted aminobicyclo[4.3.0]nonanes in good yields. To explore the late stage diversification of these compounds, further work investigated a one-pot synthesis of a benzyldimethylsilyl-derived analogue. The synthetic utility of this compound was demonstrated using C–C bond coupling reactions, for the late stage synthesis of a range of sp3-rich bicyclononane scaffolds with up to six stereogenic centres. The second section of this thesis describes the development of a one-pot two-step procedure for aryl C–H amination using iron and copper catalysis. Firstly, a mild and highly regioselective method for the bromination (and chlorination) of arenes via iron(III) triflimide activation of N-bromosuccinimide (or N-chlorosuccinimide) was developed. The scope of both processes was explored for the synthesis of a wide range of aromatic compounds and natural products. The one-pot iron(III)- catalysed bromination/Cu(I)-catalysed N-arylation was then studied. After optimisation, the one-pot two-step process allowed the synthesis of a large library of para-aminated aryl compounds in high yields as single regioisomers.
14
Hilpmann, Gerd [Verfasser]. "Process Intensification via Catalytic One-Pot Conversion of Hemicelluloses to Sugar Alcohols / Gerd Hilpmann." Aachen : Shaker, 2017. http://d-nb.info/1138177113/34.
15
Balas, Matthieu. "Sustainable catalytic process for the one-pot formation of cyclic carbonates through oxidation of alkenes and CO2 cycloaddition." Electronic Thesis or Diss., Sorbonne université, 2021. http://www.theses.fr/2021SORUS068.
Abstract:
Ce projet a pour objectif la mise au point d’une réaction globale de synthèse de styrène carbonate à partir du styrène en présence de CO2 et d’un oxydant propre : O2. Les catalyseurs Salophen-R-M (R = Me2N, Et2N, tBu et M = Mn, Ni et Cr) ont été synthétisés et leur activité co-catalytique pour la réaction de cycloaddition de CO2 sur le styrène oxyde a été évaluée en présence de Bu4NBr ; Salophen-Me2N-Cr a présenté les meilleurs résultats : 99% de rendement obtenu après 3h à 80°C. Les complexes Salophen-R-M ont été greffés sur silice mésoporeuse {NH2}-SBA-15 par liaison covalente. En parallèle, le greffage de sels d’ammonium quaternaires a été optimisé par voie ex-situ sur SBA-OH. Ces matériaux catalytiques ont été testés pour la formation de styrène carbonate, avec des rendements supérieurs à ceux obtenus en solution grâce à l’effet de synergie lié à la présence de silanols. Le catalyseur Salophen-Me2N-Cr a été testé en réaction d’époxydation Mukaiyama du styrène en présence de O2 Un rendement en styrène oxyde de 50% a été obtenu dans des conditions de réaction similaires à celles utilisées en cycloaddition. La réaction globale a été effectuée en présence de catalyseurs Bu4NBr et Salophen-Me2N-Cr à 80°C sous 3,5 bar O2 et 11 bar CO2. Un rendement maximum en styrène carbonate de 31% a été obtenu après réaction en deux étapes distinctes d’oxydation (3h) puis de cycloaddition (20h)The objective of this project is to develop a comprehensive reaction for the synthesis of styrene carbonate from styrene in the presence of CO2 and a clean oxidant: O2. Salophen-R-M (R = Me2N, Et2N, tBu and M = Mn, Ni and Cr) catalysts were synthesized and their co-catalytic activity for the cycloaddition reaction of CO2 on styrene oxide was evaluated in the presence of Bu4NBr; Salophen-Me2N-Cr showed the best results: 99% yield obtained after 3h at 80°C. Salophen-R-M complexes were grafted onto mesoporous silica {NH2}-SBA-15 by covalent bonding. In parallel, the binding of quaternary ammonium salts was optimized by ex-situ grafting on SBA-OH. These catalytic materials were tested for the formation of styrene carbonate, with yields higher than those obtained in solution thanks to the synergy effect linked to the presence of silanols. The Salophen-Me2N-Cr catalyst was tested in the Mukaiyama epoxidation reaction of styrene in the presence of O2. A 50% yield of styrene oxide was obtained under reaction conditions similar to those used in cycloaddition. The overall reaction was performed in the presence of Bu4NBr and Salophen-Me2N -Cr catalysts at 80°C under 3.5 bar O2 and 11 bar CO2. A maximum yield of styrene carbonate of 31% was obtained after a two-step reaction of oxidation (3h) and cycloaddition (20h)
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Carvalho, Rocha Catarina. "Towards a catalytic system allowing the "one-pot" conversion of alkenes into cyclic carbonates in the presence of dioxygen/carbon dioxide mixtures." Paris 6, 2013. http://www.theses.fr/2013PA066758.
Abstract:
This work aims to develop a heterogeneous catalyst for the direct conversion of an alkene to the corresponding cyclic carbonate in the presence of O2 and CO2. A MnIII salen complex and quaternary ammonium salts (QAS) bearing a -(CH2)2OH function were considered as active phases for the epoxidation and epoxide cyclocarbonatation, respectively. The activity of several QAS was measured to study the influence of the ammonium structure, as well as that of counter-ions. The C16H33N(CH3)2(CH2CH2OH)+Br- salt (HEA16Br) turned out to be more active than choline chloride (HEA1Cl). DFT calculations were used to support the influence of the -(CH2)2OH function and the unexpected reactivity of the HCO3- ion. SBA-15-type materials bearing CxHyN(CH3)2(CH2CH2OH)+ groups were obtained by: i) the impregnation of Al-SBA-15 by aqueous HEA16Cl or ii) covalent anchoring of -C3H6N(CH3)2(CH2CH2OH)+Cl- (HEA3Cl) groups on SBA-15. In both cases, the yields of cyclic carbonate were higher than those obtained in solution, a priori because of a synergistic effect due to the presence of silanols. The catalytic performances of MnIII complex, anchored onto silica through i) dihydroimidazole or ii) phosphonate ligands, were equivalent to that measured in solution, but with a high rate of leached active species. Finally, preliminary "one-pot" studies, involving ,simultaneously, the MnIII salen complex and HEA1Cl with an O2/CO2 mixture were carried out with an in-situ temperature variation from 80 to 120°C. Under these conditions, it appeared that the sacrificial aldehyde not consumed in the epoxidation step could induce side reactionsCes travaux visent à mettre au point un catalyseur hétérogène permettant la transformation directe d’un alcène en son carbonate cyclique en présence d’O2 et de CO2. Un complexe salen du MnIII et des sels d’ammonium quaternaires (SAQ) porteurs de groupements -(CH2)2OH ont été considérés comme phases actives pour les réactions d’époxydation et de cyclocarbonatation des époxydes, respectivement. L’activité de nombreux SAQ a été mesurée afin d’étudier l’influence de la structure de l’ammonium ainsi que des contre-ions. Le sel C16H33N(CH3)2(CH2CH2OH)+Br- (HEA16Br) est plus actif que la choline (HEA1Cl). Les calculs DFT ont permis d’étayer l’influence du groupement -(CH2)2OH ainsi que la réactivité particulière de l’ion HCO3-. Des matériaux siliciques de type SBA-15 porteurs de groupements CxHyN(CH3)2(CH2CH2OH)+ ont été obtenus : i) par imprégnation de Al-SBA-15 par HEA16Cl, ii) par ancrage covalent de groupements -C3H6N(CH3)2(CH2CH2OH)+Cl- (HEA3Cl) sur SBA-15. Dans les deux cas, les rendements en carbonate cyclique sont supérieurs à ceux obtenus en solution, a priori en raison d’un effet de synergie lié à la présence de silanols. Le complexe de MnIII ancré sur silice par le biais de ligands : i) dihydroimidazole, ii) phosphonate a donné des activités équivalentes à celle mesurée en solution mais avec un fort taux de lessivage de la phase active. Enfin, les premières études « one-pot » impliquant simultanément le salen du MnIII et HEA1Cl avec un mélange O2/CO2 ont été réalisées en faisant varier la température de 80 à 120°C en cours de réaction. Dans ces conditions, il apparait que l’aldéhyde sacrificiel non consommé lors de l’étape d’époxydation induit des réactions secondaires
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Jasselin-Hinschberger, Adeline. "Polyfonctionnalisations sélectives par voie organométallique en série furopyridines : développement de procédés séquentiels et "one-pot" originaux." Thesis, Université de Lorraine, 2014. http://www.theses.fr/2014LORR0163/document.
Abstract:
Le travail décrit dans ce mémoire concerne l'étude de la métallation régiosélective d’un bicycle fusionné: la furo[3,2-B]pyridine. L'influence de la nature du système basique sur le cours de la réaction et sur la régiosélectivité de la lithiation a été étudiée avec différentes bases : n-BuLi, LiTMP, LiDA et [n-BuLi/LiDMAE]. D'un point de vue fondamental, cette étude nous a permis d'établir quelques règles pour la fonctionnalisation des furopyidines, ce qui nous a conduit à l'obtention efficace et rapide d'une vaste chimiothèque de furo[3,2-B]pyridines polyfonctionnalisées et refonctionnalisables. Quelques composés préparés ont ainsi été mis en jeu dans des réactions de couplage catalysées par les métaux de transition (Pd, Ni). Deux séquences originales de lithiations en « one-Pot » ont également été développées et permettent l’obtention de squelettes furopyridiniques hautement fonctionnalisés avec d’excellents rendementsThe work described in this PhD thesis concerns the regioselective metalation study of a fused heterocycle : the furo[3,2-B]pyridine. The influence of the basic system on the reaction and on the regioselectivity of the lithiation has been studied with several bases : n-BuLi, LiTMP, LiDA and [n-BuLi/LiDMAE]. From a fundamental point of view, this study allowed us to establish some rules concerning the functionalization of furopyridines and to obtain a chemical library of various polyfunctionalized furo[3,2-B]pyridines, in good overall yields. Some of the compounds synthesized in this way, were engaged as substrate in metallo-Catalysed cross-Coupling reactions. Two efficient one-Pot multiple lithiations processes have been developed and lead to highly substitued furopyridinic scaffolds in excellent yields
18
Bassoude, Ibtissam. "Synthèse de nouveaux dérivés pyrazolo[1,5-a]pyrimidiniques à visée biologique." Phd thesis, Université d'Orléans, 2012. http://tel.archives-ouvertes.fr/tel-00789954.
Abstract:
Nos travaux de thèse portent sur la mise au point de nouvelles méthodes de synthèse permettant l'accès de façon rapide et efficace à différents dérivés pyrazolo[1,5-a]pyrimidiniques diversement fonctionnalisés.La première partie de ce travail concerne l'étude et l'application de la condensation de la pyran-2-one avec les 5(3)-amino-3(5)-arylpyrazoles que ce soit par chauffage classique ou sous irradiation micro-onde. Par la suite, un nouveau procédé d'(hétéro)arylation pallado-catalysé direct régiosélectif a été mis à profit pour élaborer des pyrazolo[1,5-a]pyrimidines fonctionnalisées tant en position 3 que sur le méthyle situé sur le sommet 7 de la 5,7-diméthylpyrazolo[1,5-a]pyrimidine.Le dernier volet de ce mémoire a été consacré à la préparation des entités pyrazolo[1,5-a]pyrimidiniques substituées en position 7 par des motifs benzyliques et ce, via une procédure " one-pot ", sous irradiation micro-onde, constituée d'une réaction d'arylation directe pallado-catalysée suivie d'une saponification-décarboxylation.
19
Boiaryna, Liliana. "Evaluation de la catalyse à l’or dans la chimie des ions N-acyliminiums : application à la synthèse one-pot de composés polycycliques azotés." Thesis, Le Havre, 2013. http://www.theses.fr/2013LEHA0008/document.
Abstract:
AGrâce à sa forte carbophilie, l’or est devenu en quelques années un métal de choix pour la formation de liaisons C-C et C-X (X = O, N, S). Par ailleurs, sa capacité à activer des hétéroatomes (acidité σ-Lewis) a été reconnue également et justifiée par de nombreux exemples de transformations de substrats carbonyles, imines, alcools π-activés et époxydes. Dans le contexte de la recherche de méthodes économiques et respectueuses de l'environnement dans le domaine de la chimie des ions N-acyliminiums, nous nous sommes intéressés à la capacité de l’or à promouvoir la formation des ions N-acyliminiums. Dans une première partie de ce travail, nous avons montré que l'acidité de type σ-Lewis de sels cationiques d’or (I) et (III) pouvait être exploitée pour catalyser efficacement la substitution nucléophile de divers alcoxy-et acétoxylactames, précurseurs d’ions N-acyliminiums. La réaction est compatible avec une large gamme de nucléophiles, incluant notamment l'allyltriméthylsilane, les éthers d'énols silylés, les arènes et les dérivés de méthylènes actifs. Dans un second temps, les deux caractères carbophile et oxophile des catalyseurs à l’or ont été combinés dans un processus cascade α-amidoalkylation/hydroarylation. Une seconde approche multicatalytique (acide de Brønsted – acide de Lewis) a ensuite été développée comme alternative pour pallier à certaines limites du système « tout or ». Ces séquences réactionnelles one-pot permettent d’accéder de façon rapide et efficace à un large panel de composés polycycliques fusionnés à partir de matières trivialesAGold catalysts, as soft carbophilic Lewis acids, have rapidly develop and mature to become nowadays an outstanding tool for new C-C and C-X bonds (X = O, S, N) through π-bond activation. Moreover, its σ-Lewis acidity was also acknowledged and exemplified by numerous examples of carbonyl, imine, π-activated alcohol and epoxide activation. As part of our ongoing studies on N-acyliminium ion chemistry, we have been interested in using gold catalysts for N-acyliminium ion generation. First, we have shown that the σ-Lewis acidity of gold(I) and gold(III) could be exploited to efficiently catalyze the nucleophilic substitution reactions of various alkoxy- and acetoxylactams, precursors of N-acyliminium ions. The reaction was found to tolerate a wide range of nucleophiles, including allyltrimethylsilane, silyl enol ethers, arenes as well as active methylene derivatives. Next, gold catalysis was applied to cascade α-amidoalkylation/hydroarylation sequences unifying both the σ- and π-Lewis acid properties of gold complexes. Alternatively, Brønsted acid/Lewis acid multicatalysis approach has been alternatively developed to override some limitations featuring this unprecedented tandem intermolecular Friedel–Crafts/intramolecular hydroarylation sequence. This two complementary and highly efficient cascade sequences enable expedient access to complex fused polycyclic structures from trivial materials
20
Ayvali, Tugce. "One-pot Synthesis And Characterization Of Colloidally Robust Rhodium(0) Nanoparticles Catalyst: Exceptional Activity In The Dehydrogenation Of Ammonia Borane For Chemical Hydrogen Storage." Master's thesis, METU, 2011. http://etd.lib.metu.edu.tr/upload/12613375/index.pdf.
Abstract:
The production of transition metal(0) nanoparticles with controllable size and size distribution are of great importance in catalysis since their catalytic activity decreases as nanoparticles aggregate into clumps and ultimately to the bulk metal. Reducing the particle size of heterogeneous catalyst provides a significant rise in its activity as the fraction of surface atoms increases with decreasing particle size. Therefore, transition metal(0) nanoparticles need to be stabilized to certain extend in their catalytic applications by strong stabilizers. In this regard, tert-butylammonium octanoate [(CH3)3CNH3+][CH3(CH2)6COO-] seems to be an appropriate stabilizer for rhodium(0) nanoparticles since octanoate anion and its associated tert-butylammonium cation can provide a sufficient protection for rhodium(0) nanoparticles against aggregation by the combined electrostatic and steric effects.
We report herein the preparation and characterization of rhodium(0) nanoparticles stabilized by tert-butylammonium octanoate and their catalytic use in the dehydrogenation of ammonia borane, H3NBH3, which appears to be the most promising hydrogen storage material due to its high hydrogen content (19.6 wt %). Rhodium(0) nanoparticles stabilized by tert-butylammonium octanoate were reproducibly prepared by the reduction of rhodium(II) octanoate dimer with tert-butylamine borane in toluene at room temperature and characterized by EA, XRD, ICP/OES, TEM, HRTEM, STEM, FTIR, XPS, UV-VIS and NMR spectroscopy. The new rhodium(0) nanoparticles is the first example of well-defined, reproducible, and isolable true heterogeneous catalyst used in the dehydrogenation of ammonia borane. They show record catalytic activity in the dehydrogenation of ammonia borane at room temperature with an apparent initial TOF value of 342 h-1 and TTO value of 1100.
21
Pantaine, Loïc. "Aminocatalyse et Réactions en Cascade pour la Synthèse de Polycycles Tridimensionnels." Thesis, Université Paris-Saclay (ComUE), 2016. http://www.theses.fr/2016SACLV084/document.
Abstract:
Les travaux exposés dans ce manuscrit ont pour objectif d’étudier des séquences réactionnelles organocatalysées permettant la formation stéréosélective de liaisons carbone-carbone ou carbone-hétéroatome. Plusieurs stratégies ont été développées pour la préparation d’architectures cycliques chirales dont la synthèse représente un enjeu important en raison de leur présence dans un grand nombre de molécules d’intérêt biologique. Le manuscrit débute par une introduction sur le principe de l’organocatalyse en se focalisant sur les différents modes d’activation en aminocatalyse.Le premier chapitre traite de la synthèse, sans solvant, régio- et diastéréosélective de bicycles comportant une hydrazine cyclique. Le deuxième chapitre combine la désaromatisation ou la désymétrisation à une séquence aminocatalysée, pour former des polycycles tridimensionnels énantio-enrichis à partir d’aldéhydes insaturés. Enfin, le troisième chapitre se concentre sur la synthèse de sulfamides non symétriques et leur utilisation comme substrats en aminocatalyseThe work presented in this manuscript aims to study organocatalytic reaction sequences enabling the stereoselective formation of carbon-carbon and carbon-heteroatom bonds. Various strategies have been developped for the preparation of chiral cyclic architectures, which represents an important challenge due to their presence in a vast number of biologically active compounds. This manuscript starts off by introducing the principal of organocatalysis, and more specifically the different activation means used in aminocatalysis.The first chapter focuses on the regio- and diastereoselective synthesis of cyclic hydrazine-containing bicycles in a solvent-free way. The second chapter merges de-aromatization or desymetrization with an aminocatalytic reaction sequence, to yield tridimensional enantioenriched polycycles from unsaturated aldehydes. Lastly, the third chapter concentrates on the synthesis of unsymmetrical sulfamides and their uses as substrates in aminocatalysis
22
Mortinho, Ana Cristina da Costa. "Novel synthetic routes towards azaindoles, Exploring one-pot metal-catalysed reactions." Master's thesis, 2018. http://hdl.handle.net/10362/53594.
Abstract:
Azaindoles are heterocyclic compounds scarce in nature, although interesting scaffolds in medicinal chemistry so there is a need of developing sustainable synthetic methods to obtain these cores. To date several methods involving more than one metal-catalysed reaction, like C-N cross-coupling,Heck coupling or the Sonogashira have been developed towards azaindoles. However, these methods require the use of amino-halopyridines as starting materials, which are difficult to prepare.
This project aimed to surpass the need of functionalization of aminopyridines conceiving a fast and scalable one-pot methodology towards azaindole synthesis.
The first strategy envisaged a well-established reaction in our group, the C-N cross-coupling reaction, to prepare an imine/enamine in situ, followed by a C-H activation / oxidative cyclization reaction catalysed by a metal. The preliminary studies were made using 2,5-dimethylaniline and α-bromo styrene and other synthetized bromides. The indole compound II.2 was isolated in 50% yield, and under the same conditions different aminopyridines and bromides were tested using palladium catalysis in an unprecedented approach for azaindole synthesis. This strategy afforded only one regioisomer, a 4-azaindole (II.4) with a 70% yield and worked only with aminopyridines that possess electro-donating groups. However, this method proved to be limited to few substrates. Thus, an alternative approach was attempted in which the imines/enamines were formed in situ by condensation of an amine with a ketone, followed by C-H activation/oxidative cyclization catalysed by palladium. Preliminary studies were carried with 2,5-dimethylaniline and acetophenone and afforded the corresponding indole II.2 in 51% yield. Next, the same strategy was applied to aminopyridines. The reaction demonstrated to be effective when acetophenones were used. Thus, a variety of 4-azaindoles (14 examples, 13 synthesized in this thesis) were synthesized by this methodology with yields ranging from 24 % up to 96%, possessing electron-withdrawing and electron donating groups. The method developed consists on a simple protocol, a one-pot reaction, involving a C-H activation reaction scarcely explored in the synthesis of this class of compounds.
23
Panteleev, Jane. "Rhodium and Palladium Catalysis in the Synthesis of Carbo- and Heterocycles." Thesis, 2012. http://hdl.handle.net/1807/34831.
Abstract:
This thesis describes the development of transition metal catalyzed transformations towards the synthesis of stereochemically rich motifs and heterocycles. The main themes present throughout this thesis are rhodium-catalysis in reactions of boronic acids with alkenes and alkynes, the use of alkynes as a key motif in the synthesis of heterocycles, and the use of domino and one-pot processes to effect high efficiency in multistep transformations.
In Chapter 1, a rhodium-catalyzed desymmetrization of diazabicyclic alkenes with boronic acids is discussed. In this work a chemodivergent and enantioselective process for the synthesis of substituted cyclopentenes and cyclopentanes is developed. Both the chemo- and the enantioselectivity of the reaction are shown to be highly dependent on the phosphine ligand structure. The observed reactivity of rhodium is further applied to a domino reaction to synthesize highly substituted benzofuranones.
In Chapter 2, the reactivity of boronic acids and alkynes under rhodium catalysis is exploited as a key step to access polycyclic motifs. In the first part of this chapter the development of a domino process using both rhodium and palladium catalysis is described. Detailed mechanistic investigations allow some insight into the interactions between two catalysts. In the last part of this chapter, preliminary experiments in the application of multimetallic catalysis in the synthesis of azadibenzoxepines are discussed.
Chapter 3 summarizes work on the arylation of propargylic alcohols with boronic acids under rhodium catalysis. This reaction is shown to proceed with high regioselectivity and can be conducted under mild conditions. The resulting allylic alcohols are shown to be versatile motifs and are applied in a synthesis of indenes and quinolines.
In the final chapter of this thesis, iodotriazoles are explored as key intermediates in the synthesis of fused triazole-containing heterocycles. Palladium-catalyzed cyclization, either through C-H functionalization or through Heck coupling, is achieved. Furthermore, it is shown that the copper-catalyzed azide-alkyne cycloaddition and palladium-catalyzed C-H arylation can be combined into a one-pot process.
24
Viduedo, Nuno André dos Santos. "Sustainable and Efficient Manganese-Catalyzed Imine Formation: a Step Further to One-Pot Bimetallic Synthesis of N-Heterocycles." Master's thesis, 2021. http://hdl.handle.net/10362/125915.
Abstract:
Imine derivatives have long been described as exceptionally useful compounds in organic chemistry, being mostly recognized as key intermediates in the synthesis of nitrogen heterocycles, such as indoles and azaindoles. In fact, these two similar N-heterocyclic scaffolds are widely present in biologically active compounds, thus considered privileged nucleus in medicinal chemistry. Therefore, there is a great interest of the scientific community in developing new synthetic methodologies to efficiently obtain both imines and the corresponding heterocyclic structures.
Recently, imine synthesis has been explored by acceptorless dehydrogenative coupling (ADC) of aromatic amines and primary alcohols, via manganese-catalyzed processes. In this thesis, several phosphine-free manganese(I) tricarbonyl complexes, bearing different bidentate ligands, were employed in order to find the most efficient ones for the ADC reaction of aniline and aminopyridine systems. In this context, manganese complexes bearing chelating di-triazole-based ligands proved to be the most appropriate. Additionally, reaction conditions were optimized to maximize imine formation. Interestingly, it was found that ADC reactions were efficiently catalyzed using 3 mol% of Mn-based catalyst loading, in the presence of potassium tert-butoxide and molecular sieves, achieving high yields (up to 99%) of a large variety of imines (more than 25), starting from aniline and aminopyridine derivatives.
Next, imine synthesis from aromatic amines and secondary alcohols, mediated by Mn-catalysts, was explored, while we were getting closer to the creation of N-heterocycles synthetic routes. Reaction conditions were separately optimized for secondary alcohol oxidation and ketimine formation, yielding the desired products in 91% and 95%, respectively. Lastly, a bimetallic route, involving manganese and palladium catalysis, to achieve indoles and azaindoles, from simple and commercially available aromatic amines and alcohols, were established. This one-pot procedure, concerning 3 reaction steps, allowed the obtention of indole scaffold in a promising 30% yield. On the other hand, although only trace amounts of azaindoles were found, the studies performed led to interesting discoveries that could be very useful in the near future.Há muito tempo que os compostos derivados de iminas são descritos como moléculas excecionalmente úteis em química orgânica, sendo maioritariamente reconhecidos como intermediários fundamentais na síntese de heterociclos de azoto, como indoles e azaindoles. De facto, estas estruturas N-heterocíclicas, semelhantes entre si, estão amplamente presentes em compostos biologicamente ativos, sendo por isso considerados núcleos privilegiados em química medicinal. Desta forma, existe um grande interesse por parte da comunidade científica no desenvolvimento de novas metodologias sintéticas para a eficiente obtenção tanto de iminas, como das respetivas estruturas heterocíclicas. Recentemente, a síntese de iminas tem sido explorada através do acoplamento desidrogenativo sem-aceitador entre aminas aromáticas e álcoois primários, por processos catalisados por manganês. Nesta tese, foram testados vários complexos tricarbonílicos de manganês(I), livres de fosfina, contendo diferentes ligandos bidentados, com o propósito de estabelecer quais os mais eficientes para este tipo de reações, em sistemas envolvendo anilinas ou aminopiridinas. Neste contexto, complexos de manganês contendo ligandos baseados no núcleo de di-triazole revelaram ser os mais adequados. Além disso, foram também otimizadas as condições reacionais de forma a maximizar a formação de imina. Interessantemente, concluiu-se que as reações de acoplamento desidrogenativo sem-aceitador eram eficientemente catalisadas usando 3 mol% de catalisador de manganês, na presença de terc-butóxido de potássio e peneiras moleculares, tendo-se alcançado rendimentos elevados (até 99%) de uma elevada variedade de iminas (mais de 25), a partir de derivados de anilinas e aminopiridinas. De seguida, a síntese de iminas a partir de aminas aromáticas e álcoois secundários, mediada por catalisadores de manganês, foi investigada, enquanto nos aproximávamos da criação de vias sintéticas para a preparação de N-heterociclos. As condições reacionais foram otimizadas separadamente para a oxidação do álcool secundário e formação da cetimina, obtendo-se os produtos desejados com 91% e 95% de rendimento, respetivamente. Por fim, foi estabelecida a via bimetálica, envolvendo catálise de manganês e paládio, para a obtenção de indoles e azaindoles, a partir de materiais de partida simples e comercialmente disponíveis, como aminas aromáticas e álcoois. Este procedimento one-pot, envolvendo 3 passos reacionais, permitiu a obtenção da estrutura de indole com um rendimento promissor de 30%. Por outro lado, embora apenas tenham sido encontradas quantidades vestigiais de azaindoles, os estudos realizados levaram a descobertas interessantes que poderão revelar-se muito úteis num futuro próximo.
25
Liou, Mei-Jyun, and 劉梅君. "One-Pot Synthesis of Quinoxalines with Hypervalent Iodine as Catalyst." Thesis, 2013. http://ndltd.ncl.edu.tw/handle/69115052672680191048.
Abstract:
碩士高雄醫學大學
醫藥暨應用化學研究所
101
Various biologically important quinoxaline derivatives were efficiently synthesized via one-pot reaction between o-phenylenediamine and internal alkynes in excellent yields. This method utilizes inexpensive, non-toxic, and environment benign hypervalent iodine source such as [(diacetoxyiodo) benzene, PhI(OAc)2, PIDA] to replace expensive metal catalysts. One of the quinoxalines i.e.45i was evaluated for leukemia cancer cell lines and turned out to be good candidate.
26
林懏濝. "One-pot synthesis of bioactive molecular fragment using iodine as catalyst." Thesis, 2005. http://ndltd.ncl.edu.tw/handle/41320355851206192840.
27
方顥伶. "One-Pot Synthesis of Bioactive Decahydroquinolines and Flavanone Derivatives Using Iodine as Catalyst." Thesis, 2007. http://ndltd.ncl.edu.tw/handle/10554964013312880949.
28
Zhan, Fu-Yu, and 詹馥瑜. "I. Synthesis and Application of Chiral Catalysts for Nazarov reactionII. One-pot synthesis of quinolinone derivative via the Ugi/ ACM/ Nazarov." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/jwufwr.
Abstract:
碩士國立東華大學
化學系
104
The first part is the synthesis of Pyridine Bis (oxazoline) (Py-Box) and Schiff-base using (+) - camphor amino-alcohol towards the catalytic approach for Asymmetric Nazarov reaction The second part is a novel one-pot 4- component Ugi reaction and the Alkyne-Carbonyl-metathesis (ACM) results in Quinoline derivative followed by Nazarov reaction
29
Wang, Yi-Fu, and 王義富. "Three-component Reaction : Efficient and Facile Method for the One-pot Synthesis ofα-Aminophosphonates using new Catalyst under Solvent-free Condition." Thesis, 2006. http://ndltd.ncl.edu.tw/handle/84580174679716917946.
Abstract:
碩士國立臺灣師範大學
化學系
94
α-Amino phosphonates can be synthesized by using carbonyl compounds (aldehyde or ketone)、aniline ,and triethylphosphite in the presence of the proper catalysts(Iodine,Trichloro-1,3,5-Triazine,Ceric Ammonium Nitrate,or Iron Chloride) under solvent-free condition at room temperature. The methodology can afford high yields of products and short reaction time compared to tranditional methods.
30
Ye, Tzuen-Yang, and 葉尊揚. "Copper-Catalysed Aerobic Oxidative Carbocyclization- Ketonization, One-Pot Synthesis of Imidazo[1,2-a]benzimidazole and 1H-pyrrol-1-yl-1H-benzo[d]imidazole-5-carboxylate." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/73013471742307853416.
Abstract:
碩士國立交通大學
應用化學系碩博士班
104
This thesis is divided into three parts, the first part is copper-catalysed aerobic oxidative carbocyclization- ketonization, one-pot synthesis of imidazo[1,2-a]benzimidazole, the second part is a single copper-catalysed aerobic oxidative carbocyclization- ketonization, one-pot synthesis of 1H-pyrrol-1-yl-1H-benzo [d] imidazole-5-carboxylates, the third part is a synthetic Rosoxacin. Part 1: Two copper metal-catalyzed alkyne-terminal addition to the imine derived from 2-aminobenzimidazole with an aromatic aldehyde formed in an oxygen system and accompanied by intramolecular cyclization synthesis benzoimidazo [1,2-a] imidazolones, on this product carbonyl newly formed from oxygen, our laboratory successfully developed a highly efficient synthesis benzoimidazo [1,2-a] imidazolones method, this method is by 2-aminobenzimidazole, aromatic aldehyde and terminal acetylene in one-pot of there oxygen conditions of the novel oxidation 5-exo-dig cyclization - ketonization, the results of this section have been published in Chem Comm 2016, 52, 6621-6624. Part 2: Obtained in the first part of the study of the side-products of the pyrrole ring, and further study of how the formation of this side-product, and make it the main product formed propargylamine single copper metal-catalyzed alkyne-terminal addition to the imine to oxygen conditions under propargylamine again with a terminal alkyne to form intermediate 44, along with the final intramolecular cyclization, synthesizing 1H-pyrrol-1-yl-1H-benzo [d] imidazole-5-carboxylates, and the newly formed on this product carbonyl from oxygen, this results in the synthesis of 1H-pyrrol-1-yl-1H-benzo [d] imidazole-5-carboxylates provides novel synthetic methods. Part 3: In the computer-aided simulation, old drugs Rosoxacin in IRAK4 (interleukin-1 receptor-associated kinase 4) has a good biological activity, IRAK4 is a protein kinase, so we have to 3-pyridin-4-ylaniline and ethoxy malonate (ethoxymethylenemalonate ester) in polyphosphate rings, then alkaline hydrolysis to give the product Rosoxacin.
31
Chiu, Feng-Yu, and 邱夆昱. "(I) Synthesis of benzimidazole linked indoline derivative by acid catalyst(II) One-pot synthesis of derivative of ellipticine which has the activity against Mycobacterium tuberculosis." Thesis, 2017. http://ndltd.ncl.edu.tw/handle/3snnw5.
Abstract:
碩士國立交通大學
應用化學系碩博士班
105
This thesis has two parts: The first part is about synthesis of benzimidazole linked indoline derivatives from C-2-linked-o-aminobenzyl benzimidazole by acid catalyst. This method can apply to various funtional groups. There is no published paper refer to benzimidazole linked indoline derivatives, so we hope these heterobicyclic molecules can show more bioactivity and also hope this thesis can open a new page for research of drugs. The second part is about One-pot synthesis of derivative of ellipticine which has the activity against Mycobacterium tuberculosis. We hope we can improve its activity of anti-TB by changing different funtional groups to study the structure–activity relationship.
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劉淑雅. "1.Aqueous Solution Synthesis of Palladium Nanocrystals with Systematic Shape Evolution and Their Facet-Dependent Catalytic Activity 2.One-Pot Synthesis of Copper Nanoparticles in Aqueous Solution." Thesis, 2014. http://ndltd.ncl.edu.tw/handle/37547828166590597065.
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HUNG, YING-CHI, and 洪英棋. "One-pot Reaction for the Synthesis of Flavones via Oxidation of Flavanones and Selective Suzuki-Miyaura Reaction to 3- and 4-Bromocoumarins Catalyzed by Water-soluble Palladium Catalyst." Thesis, 2019. http://ndltd.ncl.edu.tw/handle/hews7c.
Abstract:
碩士國立臺北科技大學
分子科學與工程系有機高分子碩士班
107
The dissertation comprises two subjects. In the first subject, we designed a Pd(OAc)2/cationic 2,2’-bipyridyl-catalytic system to catalyzed conjugate addition of chromones and arylboronic acids forming flavanone derivatives as the first step of one-pot reaction, in second step adding iodine which undergoes oxidation of flavanone to obtain flavone product. Then the foregoing flavone derivatives proceeded with demethylation to acquire flavone nature products and medical potential flavone derivatives. In the second subject, our research was aimed to exploit water-soluble palladium catalyst to conduct selective Suzuki-Miyaura reaction of 3- and 4-bromocoumarins and arylboronic acids in water through different temperatures and bases. Next we carried out asymmetric Suzuki-Miyaura reaction to 3.4-dibromocoumarin by one-pot reaction in water and thereby gaining various coumarin derivatives.
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Hsu, Che-Hao, and 許哲豪. "Synthesis of Benzol Pyran Fused Carbazole Derivatives through Pictet-Spengler Reaction and Synthesis of the 4-Benzylidene-3,6-di-phenylhex-2-en-5-ynal Deriva- tives via One-Pot Palladium Catalysed Sonogashira and Hydroalkynylation Cascade Reactions." Thesis, 2014. http://ndltd.ncl.edu.tw/handle/99080233803268094885.
Abstract:
碩士國立臺灣師範大學
化學系
102
This thesis consists two parts. In which the first part of thesis describes the preparation of benzopyran fused carbazole derivatives from (2R,3R,4S)-4-(1H-indol-3-yl)-2-phenylchroman-3-amine through Pictet-Spengler reaction. A wide variety of benzopyran fused carbazole derivatives were synthesized in this process in good to moderate yields. The second part deals with the Pd catalyzed one pot Sonogashira and hydroalkynylation cascade reactions to the synthesis of the 4-benzylidene-3,6-diphenylhex-2-en-5-ynal derivatives. This is an unprecedented result where the addition of two alkyne units to the parent 3-bromo-3-phenylacrylaldehyde to obtain substituted hex-2-en-5-ynal derivatives in good yields. High functional group tolerance, simple and mild reaction conditions are important features in this reaction. Keyword Part I: Pictet-Spengler reaction Benzopyran fused carbazole Pyrido indole Chroman amine Piperidine Part II: Pd catalyzed Sonogashira and hydroalkynylation cascade reactions Indenone Pyridine Indole Carbazole