Дисертації з теми "C-C bond catalysis"
Оформте джерело за APA, MLA, Chicago, Harvard та іншими стилями
Ознайомтеся з топ-50 дисертацій для дослідження на тему "C-C bond catalysis".
Біля кожної праці в переліку літератури доступна кнопка «Додати до бібліографії». Скористайтеся нею – і ми автоматично оформимо бібліографічне посилання на обрану працю в потрібному вам стилі цитування: APA, MLA, «Гарвард», «Чикаго», «Ванкувер» тощо.
Також ви можете завантажити повний текст наукової публікації у форматі «.pdf» та прочитати онлайн анотацію до роботи, якщо відповідні параметри наявні в метаданих.
Переглядайте дисертації для різних дисциплін та оформлюйте правильно вашу бібліографію.
Rousseaux, Sophie. "Palladium-Catalyzed C(sp2)-C(sp3) Bond Formation." Thèse, Université d'Ottawa / University of Ottawa, 2012. http://hdl.handle.net/10393/23058.
Повний текст джерелаLomas, Sarah. "C-C bond forming catalysis with alkaline earth acetylides." Thesis, University of Bath, 2013. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.604644.
Повний текст джерелаFossey, John Stephen. "Group 10 NCN pincer complexes for C-C bond forming catalysis." Thesis, Queen Mary, University of London, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.409665.
Повний текст джерелаSzymaniak, Adam Anthony. "Nonracemic Organoboronates by Transition Metal-Catalyzed C-C and C-Si Bond Forming Reactions." Thesis, Boston College, 2018. http://hdl.handle.net/2345/bc-ir:108119.
Повний текст джерелаThis dissertation will describe the development of three transition metal-catalyzed syntheses of nonracemic organoboronates. The first chapter explains the development of a palladium-catalyzed enantiotopic-group-selective cross-coupling of geminal bis(boronates) with alkenyl electrophiles. This process enables the synthesis of highly valuable nonracemic disubstituted allylic boronates. Chapter two describes a palladium-induced 1,2-metallate rearrangement of vinylboron “ate” complexes. The newly developed process incorporates an alternative route for the transmetallation step of Suzuki-Miyaura cross-couplings. Lastly, an enantioselective platinum-catalyzed hydrosilylation of alkenyl boronates is disclosed. This reaction enables the synthesis of nonracemic geminal silylboronates for the divergent synthesis of functionalized
Thesis (PhD) — Boston College, 2018
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Chemistry
Wilkinson, Matthew. "Bulky arylphosphines and arylarsines for catalysis of C-C bond-forming reactions." Thesis, University of Bristol, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.274605.
Повний текст джерелаTruscott, Fiona Rosemary. "Transition metal catalysed C-C bond formation via C-H functionalisation." Thesis, University of Oxford, 2012. http://ora.ox.ac.uk/objects/uuid:6a1ef296-8d63-470d-96bd-3e01a887c81f.
Повний текст джерелаZárate, Sáez Cayetana. "C-heteroatom bond-formation via ni-catalyzed c-o bond cleavage." Doctoral thesis, Universitat Rovira i Virgili, 2017. http://hdl.handle.net/10803/401555.
Повний текст джерелаA pesar de que el campo del acoplamiento cruzado ha desarrollado increíbles avances, la gran mayoría de procesos todavía se basa en el uso de halogenuros de arilo. Sin embargo, este tipo de electrófilos presentan una toxicidad intrínseca y, a su vez, su síntesis resulta tediosa, especialmente cuando se trata de halogenuros de arilo altamente funcionalizados. Debido a ello, la comunidad sintética se ha volcado en la búsqueda de alternativas al uso de halogenuros de arilo en química de acoplamiento cruzado. Un gran esfuerzo se ha desarrollado en la última década para implementar los derivados del fenol en este tipo de transformacions debido a la abundancia natural y comercial de dichos compuestos y a su baja toxicidad en comparación con los organohalogenuros. Sin embargo, la alta energía de activación necesaría para romper los enlaces C-O ha limitado considerablemenete el uso de derivados del fenol en reacciones de acomplamineto cruzado, sobre todo si se trata de éteres de metilo. Actualmente la gran mayoría de métodos basados en esta familia de electrófilos se utilizan en la formación de enlaces C-C. De lo contrario, apenas existen técnicas para obtener enlaces C-heteroátomo probablemente debido a la baja reactividad de los nucleófilos donde la densidad de carga negativa reside en un heteroátomo. La presente tesis docotoral se ha centrado en el desarrollo de nuevas metodologías para la creación de enlaces de tipo C-heteroatomo mediante la activción catalítica de enlaces C-O con complejos de Ni. Se han descrito novedosos métodos de sililación y borilación de ésteres y metil éteres de arilo y bencilo. Dichos métodos suponen una via alternativa para la síntesis de silanos y boronatos, los cuales son intermedios de gran utilidad en síntesis orgánica. Además, el descubrimiento de unas condiciones totalmente inusuales para activar enlaces de tipo C-OMe ha abierto nuevas perspectivas sobre la reactividad de este tipo de enlaces y, a la vez, ha sugerido la existencia de nuevos mecanismos de activación.
While the field of cross-coupling has reached remarkable levels of sophistication, the vast majority of processes are still being conducted with organic halide counterparts. Drawbacks associated to their toxicity and the limited accessibility of densely functionalized aryl halides have prompted chemists to develop powerful, yet practical, alternatives. Among these, the utilization of phenol derivatives as coupling partners via C-O bond cleavage would be particularly rewarding due to their readily availability and benign nature. However, the high activation energy required for effecting C–O bond cleavage has become a daunting challenge when devising catalytic techniques using phenol derivatives, specially always-elusive aryl methyl ethers. At present, the vast majority of cross-coupling reactions using phenol derivatives remains confined to C–C bond formation, whereas the formation of C-heteroatom bonds has been poorly studied, likely due to the less reactivity of heteroatom-based nucleophiles. This doctoral thesis has focused on the development of new methodologies for forging C-heteroatom bonds via Ni-catalyzed C-O bond cleavage. It has been described new protocols for the silylation and borylation of aryl and benzyl esters and methyl ethers. These methodologies can be used as useful alternatives towards the synthesis of aryl and benzyl silanes and boronates, incredible important intermediates in organic synthesis. Furthermore, the discovery of unusual, yet surprising, conditions for the cleavage of C-OMe bonds have opened up new vistas towards the reactivity of aryl and benzyl methyls ethers while suggesting new activation pathways.
Bartoszewicz, Agnieszka. "Transition metal-catalysed hydrogen transfer processes for C-C and C-N bond formation : Synthetic studies and mechanistic investigations." Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2012. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-81596.
Повний текст джерелаMazzarella, Daniele. "C-C and C-B Bond Forming Strategies Driven by the Photoexcitation of Organocatalytic Intermediates." Doctoral thesis, Universitat Rovira i Virgili, 2020. http://hdl.handle.net/10803/669808.
Повний текст джерелаEl principal objetivo científico de mis estudios de doctorado fue demostrar que la reactividad en estado excitado de los intermedios organocatalíticos son capaces de proporcionar nuevas oportunidades para desarrollar nuevas reacciones catalíticas mediante radicales para la formación de enlaces C-C y C-B. La fotoexcitación de intermedios organocatalíticos proporcionaron radicales mediante transferencia de un solo electrón u homólisis. En el Capítulo II, analizo el desarrollo de una funcionalización asimétrica organocatalítica fotoquímica de C-H del tolueno y derivados. Nuestro sistema aprovecha las propiedades oxidativas mejoradas de los iones de iminio quirales excitados con luz visible y el carácter básico de sus contraaniones para activar, a través de una transferencia de electrones acoplada a protones multisitio, derivados de tolueno. El radical resultante es atrapado más tarde por el intermedio organocatalítico quiral con alto estereocontrol. En la segunda parte de mis estudios de doctorado, me concentré en la generación catalítica de compuestos fotolábiles basados en tiocarbonilo para promover la formación de enlaces C-B y C-C. Como se detalla en el Capítulo III, empleamos un organocatalizador nucleofílico de anión ditiocarbonilo para activar electrófilos de alquilo a través de una vía SN2. El producto intermedio resultante que absorbe fotones, tras la absorción de luz visible, genera radicales a través de la escisión homolítica del enlace C-S débil. El radical generado es entonces interceptado por bis(catecolato)diboro para proporcionar productos de éster alquilborónico. El Capítulo IV destaca cómo este enfoque fotolítico se expandió a la activación de los cloruros de acilo y carbamoilo a través de una vía de sustitución de acilo nucleofílica. Los radicales acilo y carbamoilo generados fotoquímicamente se han utilizado en reacciones de tipo Giese con olefinas pobres en electrones para formar nuevos enlaces C-C. Una investigación mecanística detallada, basada en análisis espectroscópicos y electroquímicos junto con la caracterización de intermedios clave, identificó una variedad de equilibrios fuera del ciclo que cooperan para controlar las concentraciones generales de los radicales, contribuyendo a la eficiencia del proceso.
The main scientific objective of my doctoral studies was to demonstrate that the excited-state reactivity of organocatalytic intermediates could provide new opportunities to develop novel catalytic radical C-C and C-B forming reactions. The photoexcitation of organocatalytic intermediates afforded radicals through either single-electron transfer or homolysis. In Chapter II, I discuss the development of an asymmetric organocatalytic photochemical C-H functionalization of toluene and derivatives. Our system harnesses the enhanced oxidative properties of visible-light excited chiral iminium ions and the basic character of their counteranions to activate, through a multisite proton coupled electron transfer, toluene derivatives. The ensuing radical is later trapped by the chiral organocatalytic intermediate with high stereocontrol. In the second part of my doctoral studies, I focused on the catalytic generation of photolabile thiocarbonyl-based compounds to promote the formation of C-B and C-C bonds. As detailed in Chapter III, we employed a nucleophilic dithiocarbonyl anion organocatalyst to activate alkyl electrophiles through an SN2 pathway. The ensuing photon-absorbing intermediate, upon visible light absorption, generates radicals through homolytic cleavage of the weak C-S bond. The generated radical is then intercepted by bis(catecholato)diboron to afford alkyl boronic ester products. Chapter IV highlights how this photolytic approach was expanded to the activation of acyl and carbamoyl chlorides through a nucleophilic acyl substitution pathway. The photochemically generated acyl and carbamoyl radicals have been used in Giese-type reactions with electron-poor olefins to form new C-C bonds. A detailed mechanistic investigation, based on spectroscopic and electrochemical analyses along with the characterization of key intermediates, identified a variety of off-the-cycle equilibriums that cooperate to control the overall concentrations of the radicals, contributing to the efficiency of the process.
Zhang, Qi. "Transition-metal-catalyzed C-F bond formation." Diss., University of Iowa, 2016. https://ir.uiowa.edu/etd/3228.
Повний текст джерелаHarkness, Gavin J. "Sequential processes using catalytic C-O bond activation." Thesis, University of St Andrews, 2018. http://hdl.handle.net/10023/12809.
Повний текст джерелаGodwin, Christopher. "Oxovanadium Complex-Catalyzed Aerobic C-C Bond Cleavage of Biomass-derived Scaffolds." Thesis, Université d'Ottawa / University of Ottawa, 2019. http://hdl.handle.net/10393/39567.
Повний текст джерелаReich, Blair Jesse Ellyn. "Cyanide-catalyzed C-C bond formation: synthesis of novel compounds, materials and ligands for homogeneous catalysis." Texas A&M University, 2005. http://hdl.handle.net/1969.1/4987.
Повний текст джерелаBayless, Michael Bruce. "New redox-active ligands on iron and cobalt for C-C bond forming reactions." Diss., Georgia Institute of Technology, 2014. http://hdl.handle.net/1853/52286.
Повний текст джерелаWang, Lianhui. "Carboxylate-Assisted Ruthenium-Catalyzed Direct C-H Bond Functionalizations." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2014. http://hdl.handle.net/11858/00-1735-0000-0022-5E47-2.
Повний текст джерелаPearson, Stephen. "High oxidation state carbene complexes for C-H bond activation catalysis." Thesis, University of Edinburgh, 2010. http://hdl.handle.net/1842/7570.
Повний текст джерелаKossen, Hanno. "Exploration of Brønsted base catalysis for formal C–H bond activations." Thesis, University of Edinburgh, 2017. http://hdl.handle.net/1842/23598.
Повний текст джерелаNagendiran, Anuja. "Catalytic reactions with palladium supported on mesocellular foam : Applications in hydrogenation, isomerization, and C-C bond forming reactions." Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2015. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-122061.
Повний текст джерелаAt the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Submitted. Paper 5: Submitted.
Snell, Robert Henry. "Development and application of asymmetric C-N bond formation." Thesis, University of Oxford, 2011. http://ora.ox.ac.uk/objects/uuid:512e617a-2b01-45f3-86ae-c0cf4b874149.
Повний текст джерелаMateo, Martínez Ana. "Computational studies of C-B bond formation reactions." Doctoral thesis, Universitat Rovira i Virgili, 2019. http://hdl.handle.net/10803/668479.
Повний текст джерелаLa gran cantidad de fluorocarbonos en la naturaleza y su estabilidad a animado a la comunidad científica a buscar nuevas metodologías para la rotura del enlace C-F de estos compuestos. De esta manera, estos fluorocarbonos pueden ser utilizados como reactivos en la síntesis orgánica. La estabilidad de los fluoruros de arilo se da por la fuerza del enlace C-F, que es el enlace simple más fuerte de la naturaleza. Ésta es su principal característica y la razón de su poca reactividad. Por este motivo, es desafiante para la comunidad científica encontrar la manera de romper el enlace C-F. De la misma forma el enlace C-O tiene características muy similares a las del C-F y por esto, se ha utilizado como alternativa para evitar residuos fluorados. Esta Tesis trata del estudio computacional de la ruptura de los enlaces C-F y C-O mediante borilaciones y catalizadas por un catalizador de níquel. Concretamente, se ha estudiado tres reacciones diferentes y las hemos comparado y buscado sus puntos en común.
The large presence of fluorocarbons in nature and its great stability encourage science community to found new methods to break the C-F bond of this compounds, because it could be used as a starting reactant in organic synthesis. The stability of aryl fluorides is given because its C-F bond is the strongest single bond in the nature. That is its principal characteristic and the reason of it lack of reactivity. For this reason, it is challenging for scientists found the manner for C-F cleavage. As the same wise, C-O becomes an alternative of C-F to avoid the fluoride waste. This Thesis is about the computational study of the C-F and C-O cleavage through the borylation catalysed by nickel catalyst. Concretely, we have studied three borylation of C-F and C-O bonds and we compared it and show what have in common the three reactions.
Li, Bin. "Ruthenium(II) catalyzed C-H bond functionalization and hydrosilylation reactions." Thesis, Rennes 1, 2013. http://www.theses.fr/2013REN1S114.
Повний текст джерелаIn this research doctoral thesis, we have shown that imines, 2-phenylpyridine, 2-phenyloxazoline, phenylpyrazole, benzo[h]quinoline led to cyclometallated ruthenium(II) complexes from [RuCl2(p-cymene)]2 and KOAc via sp2 C-H bond activation. [RuCl2(p-cymene)]2 /KOAc/PPh3 is an efficient catalytic system for diarylation of imines and 2-phenyloxazolines in water, which gave higher activity than in organic solvents. Bulky amines were then synthesized through sequential catalytic C-H arylation and hydrosilylation of imines using [RuCl2(p-cymene)]2 catalyst. Challenging selective mono arylation of 2-pyridyl arylketones, leading to six-membered ruthenacycle intermediate, difficult to perform, was achieved with in situ generated Ru(O2CC6H4CF3)2(p-cymene) catalyst. The direct dehydrogenative oxidative alkenylation of aryloxazolines with styrenes and acrylates was catalyzed by [RuCl2(p-cymene)]2/BNPAH (1,1′-binaphthyl-2,2′- diylhydrogenophosphate) catalytic system in the presence of Cu(OAc)2.H2O as an oxidant in air. Tandem catalytic oxidation of 2-pyridylmethanols and selective sp3 C-H (mono or di) α-alkylation of 2-pyridyl ketones with functional alkenes was performed by using [RuCl2(p-cymene)]2 complex in the presence of Cu(OAc)2.H2O in DCE or toluene. In the second part, it is shown that, [RuCl2(p-cymene)]2 is a very efficient catalyst for the hydrosilylation of imines and primary amides. A wide range of aldimines and ketimines were successfully reduced to corresponding amines in high chemoselectivity by using PMHS as greener silane in ethanol at RT. Moreover, challengingly, primary amides could be selectively converted by hydrosilylation to the secondary amines under solvent free conditions
Afewerki, Samson. "Development of catalytic enantioselective C-C bond-forming and cascade transformations by merging homogeneous or heterogeneous transition metal catalysis with asymmetric aminocatalysis." Doctoral thesis, Mittuniversitetet, Avdelningen för naturvetenskap, 2014. http://urn.kb.se/resolve?urn=urn:nbn:se:miun:diva-23605.
Повний текст джерелаVuong, Khuong Quoc Chemistry Faculty of Science UNSW. "Metal complex catalysed C-X (X = S, O and N) bond formation." Awarded by:University of New South Wales. Chemistry, 2006. http://handle.unsw.edu.au/1959.4/23015.
Повний текст джерелаCai, Yingxiao. "Cobalt-catalyzed carbon-carbon bond formation by activation of carbon-halogen or carbon-hydrogen bonds." Thesis, Université Paris-Saclay (ComUE), 2016. http://www.theses.fr/2016SACLX039/document.
Повний текст джерелаThis thesis presents the development of cobalt-catalyzed carbon-carbon bonds formation. The first chapter describes a novel cobalt-catalyzed electrophilic cyanation of arylzinc species, employing benign and non-toxic N-cyano-N-phenyl-p-methylbenzenesulfonamide (NCTS) as the cyano source. In this reaction, cobalt catalyzes both the formation of arylzinc species and the cyanation reaction. Various benzonitriles are synthesized affording good to excellent yields. Using cobalt-bipyridine complexes instead of CoBr2, ketone and nitrile groups can be tolerated. The second chapter reports cobalt-catalyzed Csp3-Csp3 homocoupling reaction. A simple catalytic system could deliver dimers of a number of alkyl halides/pseudohalides and allylic acetates. Sodium iodide is crucial for the homocoupling of unactivated alkyl chlorides and tosylates. This method is extended to alkyl-alkyl cross-coupling; however, the conditions still need to be optimized. The third chapter describes a cobalt-catalyzed vinyl-benzyl cross-coupling. A variety of functionalized vinyl bromides and benzyl chlorides are efficiently coupled under mild conditions in good to excellent yields, with retention of Z/E configuration. A few mechanistic experiments indicate a single electron transfer involved. The last chapter discusses the progress on the cobalt-catalyzed arylation of 2-phenylpyridine with an arylzinc species by C-H activation and promising results are obtained
Diers, Emelyne. "Ruthenium-Catalyzed Synthesis of Biaryls through C–H Bond Functionalizations." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2013. http://hdl.handle.net/11858/00-1735-0000-0001-BC4E-F.
Повний текст джерелаLapointe, David. "Part A: Palladium-Catalyzed C–H Bond Functionalization Part B: Studies Toward the Synthesis of Ginkgolide C using Gold(I) Catalysis." Thesis, Université d'Ottawa / University of Ottawa, 2012. http://hdl.handle.net/10393/20642.
Повний текст джерелаBruneau, Alexandre. "Développement de nouvelles réactions métallo-catalysées pour la création de liaisons C-C et C-hétéroatomes : Application à la synthèse d’inhibiteurs de la Hsp90 et aux ligands de la lectine A." Thesis, Université Paris-Saclay (ComUE), 2015. http://www.theses.fr/2015SACLS138.
Повний текст джерелаThe work reported in this dissertation concerns the development of new metal-catalyzed reactions for the creation of carbon-heteroatom and carbon-carbon bonds as well as their applications to the synthesis of biologically active products.The first part of this manuscript is devoted to the study of the reactivity of sugars as nucleophiles in organometallic couplings. Conditions were developed for the creation of the C-S bond between glycosyl thiols and aryl partners. Moreover, the creation of the nitrogen carbon bond of glycosyl amine with boronic acids was studied. The products synthesized in this first part have been evaluated for their potential to inhibit the lectin A, in Pseudomonas aeruginosa related lung infections.The second part of this work is dedicated to the creation of a new series of 6BrCaQ analogues as Hsp90 inhibitors and their biological evaluation. This new series was synthetized through a new CH activation methodology. The antitumoral potential was evaluated and will be presented in this manuscript
Zhao, Liqin. "Palladium-catalyzed direct arylation via sp² and sp³ C-H activation of hetero(aromatics) and hydrocarbons for C-C bond formation." Thesis, Rennes 1, 2014. http://www.theses.fr/2014REN1S038/document.
Повний текст джерелаDuring this thesis, we were interested in the sp² and sp³ C-H bond activation catalyzed by palladium catalysts for the preparation of (hetero)aryl-aryls and biaryls. This method is considered as cost effective and environmentally attractive compared to the classical couplings such as Suzuki, Heck, or Negishi. First we described the palladium-catalyzed direct C2-arylation of benzothiophene in the absence of phosphine ligand with high selectivity. We also demonstrated that it is possible to active both C2 and C5 C-H bonds for access to 2,5-diarylated compounds in one step, and also to non-symmetrically substituted 2,5-diarylpyrroles via sequential C2 arylation followed by C5 arylation. We also studied the reactivity of polychlorobenzenes via palladium-catalyzed C-H activation. We finally examined the palladium-catalysed selective sp² and sp³ C-H bond activation of guaiazulene. The selectivity depends on the solvent and base: sp² C2-arylation (KOAc in ethylbenzene), sp² C3-arylation (KOAc in DMAc) and sp³ C4-Me arylation (CsOAc/K₂CO₃ in DMAc). Through this method, a challenging sp³ C-H bond was activated
Liu, Cong. "Transition Metal Mediated C-o Bond Cleavage: From Co2 Activation to Lignin Degradation." Thesis, University of North Texas, 2013. https://digital.library.unt.edu/ark:/67531/metadc283790/.
Повний текст джерелаBorràs, Noguera Carlota. "Sustainable and cost-effective development of chiral metal-catalysts for C-H and C-X bond forming reactions." Doctoral thesis, Universitat Rovira i Virgili, 2018. http://hdl.handle.net/10803/664741.
Повний текст джерелаLa obtención de compuestos enantioméricamente puros se ha convertido una necesidad que ha conducido a un importante progreso en la catálisis asimétrica, principalmente usando compuestos organometalicos quirales. Entre las diferentes estrategias en la optimización de los catalizadores para conseguir elevadas selectividades y actividades, el diseño y la correcta selección de ligandos quirales, modificando sus propiedades es fundamental y la más utilizada. Que un ligando sea fácil de sintetizar a partir de compuestos de partida accesibles y que estos ligandos sean estables y fáciles de manipular, tienen un elevado interés en la industria. En este contexto, el principal objetivo de esta tesis es la síntesis de distintas familias de ligandos quirales, cumpliendo con los requisitos previamente mencionados, y su posterior aplicación en distintas reacciones asimétricas de alto interés industrial: hidrogenación de alquenos funcionalizados y no funcionalizados catalizados por Rh y Ir, hidrogenación de cetonas catalizada por Ir, reacciones de substitución alílica catalizada por Pd y reacciones de substitución propargílica catalizada por Cu. Se han sintetizado diferentes familias de ligandos Fosfito/fosfinito-tioéter/selenoéter, carbeno-tioéter, amino-fosfito/fosfinito/fosfina, y varias familias de ligandos tridentados.
The obtaining of enantiomerically pure compounds has become a need that led to an important progress in asymmetric catalysis, mainly using organometallic chiral compounds. Among different strategies to optimize catalysts in order to obtain high selectivities and activities, the design and the correct selection of chiral ligands, modifying their properties, is fundamental and the most used strategy. Ligands easy to synthesize from readily accessible starting material and stable and easy to manipulate ligands, have a high interest in the industry. In this context, the main objective of this thesis is the synthesis of different chiral ligand families, according to the previously mentioned requirements, and their application in different asymmetric reactions with high industrial interest: Rh- and Ir-catalyzed hydrogenation of functionalized and minimally functionalized olefins; Ir-catalyzed hydrogenation of simple ketones; Pd-catalyzed asymmetric substitution of allylic acetates and Cu-catalyzed propargylic substitution. There have been synthesized different phosphite/phosphinite-thioether/selenoether, carbene-thioether, amino-phosphite/phosphinite/phosphine and various tridentated ligand families.
Bosnidou, Alexandra Eleni. "New Methodology for C-N Bond Formation within Iodine Redox Manifolds." Doctoral thesis, Universitat Rovira i Virgili, 2019. http://hdl.handle.net/10803/668478.
Повний текст джерелаEn esta Tesis Doctoral se describen los últimos avances en el campo de la construcción de enlaces carbono-nitrógeno. En ella se discuten alternativas más verdes, comparadas con las metodologías más comunes, mediante el uso de reactivos hipervalentes de yodo y yodo molecular como principales promotores. En la primera sección se presenta el uso de reactivos hipervalentes de yodo que promueven la aminacion C-H directa y selectiva del grupo indol en varios derivados de triptamina. A partir de esta aminación general, otras transformaciones, tales como iodinación, fluorinación, etc. fueron llevadas a cabo, obteniendo productos altamente funcionalizados con una remarcable alta quimioselectividad. De este modo, una alta diversificación estructural de derivados de triptamina están disponibles, proveyendo diferentes componentes que permiten futuras exploraciones en este área. En la siguiente sección, se describe la aminación fotoquímica y catalítica de arenos. Esta reacción funciona mediante catálisis de yodo molecular en presencia de luz visible como iniciador, dando acceso a un amplio rango de arilaminas con diferentes patrones de substitución. Esta metodología es muy general y puede expandirse a derivados con silicio que dan lugar a heterociclos de siete miembros. La ruptura de este enlace silicio-carbono da acceso a las correspondientes anilinas meta-subtituidas. La aminación directa de enlaces C-H alifáticos es una de las transformaciones más dificiles de conseguir en química orgánica. En la última parte de esta Tesis se describe la aminación intermolecular de C(sp3)-H basada en la recientemente desarrollada versión intramolecular. Esta estrategia sintética permite el acceso a diferentes estructuras aminadas de importancia. También se presenta la extensión de esta metodología hacia la aminacion de multiples C-H, obteniendo aza-heterociclos. La utilidad práctica de esta metodología esta demostrada mediante la síntesis de cuatro compuestos de interés farmacéutico
The latest developments in the field of oxidative carbon-nitrogen bond construction are represented in this Doctoral Thesis. Greener alternatives to established synthetic methodologies have been disclosed with the use of hypervalent iodine reagents and molecular iodine as main promoters. Initially, the use of defined hypervalent iodine reagents that promote the selective direct C-H-amination at the indole core of various tryptamines is presented. Starting from the general amination, subsequent transformations, such as iodination, fluorination etc. were performed to afford higher-functionalized products with a noteworthy chemoselectivity. Consequently, a higher degree of structural diversification has become available for tryptamine derivatives, providing building blocks that open chemical space for further exploration. Subsequently, a photochemical catalytic amination of arenes is discussed. The reaction proceeds under benign iodine catalysis in the presence of visible light as the initiator and provides access to a range of differently substituted arylamines. The broad scope of the reaction could further be expanded to silyl-tethered derivatives, which undergo intramolecular amination to give rise to seven-membered heterocycles. Cleavage of the silicon tether provides access to the corresponding 3-substitued anilines. The direct amination of aliphatic C-H bonds has remained one of the most challenging transformations in organic chemistry. In the last part of this thesis, the elusive intermolecular C(sp3)-H amination based on a unique homogeneous iodine catalyst system is reported. This practical synthetic strategy allows the access to aminated building blocks. An extension that fosters innovative multiple C-H amination toward aminated heterocycles is also presented. The synthetic utility of the methodology is demonstrated by the synthesis of four relevant pharmaceuticals.
Olsson, Vilhelm. "Development of New Synthetic Routes to Organoboronates by Catalytic Allylic Substitution and C-H bond Functionalization." Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2009. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-27753.
Повний текст джерелаBalzarek, Christoph. "Reactivity and mechanisms in aqueous organometallic chemistry : C-H bond activation in water catalyzed by molybdocenes /." [Eugene, Or. : University of Oregon Library System], 2000. http://libweb.uoregon.edu/UOTheses/2000/balzarekc00.pdf.
Повний текст джерелаBalzarek, Christoph 1972. "Reactivity and mechanisms in aqueous organometallic chemistry: C-H bond activation in water catalyzed by molybdocenes." Thesis, University of Oregon, 2000. http://hdl.handle.net/1794/142.
Повний текст джерелаA print copy of this title is available through the UO Libraries under the call number: SCIENCE QD412.M7 B35 2000
The chemistry of three organometallic systems in water was studied with the goal of understanding more fully the reactivity of organometallic complexes in aqueous environments. Molybdocene complexes were found to catalyze C-H bond activation reactions in water. The catalytically active solutions were prepared from the molybdocene dimer [Cp
Hofmann, Nora. "Carboxylate-Assisted Ruthenium-Catalyzed C-H Bond meta-Alkylations and Oxidative Annulations." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2013. http://hdl.handle.net/11858/00-1735-0000-0014-D4A4-1.
Повний текст джерелаZiadi, Asraa. "Metal-catalyzed functionalization of c-c bonds in four-membered rings." Doctoral thesis, Universitat Rovira i Virgili, 2014. http://hdl.handle.net/10803/320185.
Повний текст джерелаRecientemente la funcionalización catalítica de enlaces C-C ha suscitado un gran interés en la comunidad científica a pesar de los retos que conlleva. Esta tesis doctoral se ha basado en diseñar nuevos procesos catalíticos para la funcionalización de enlaces C-C en anillos de cuatro miembros. Específicamente, se ha demostrado la viabilidad de preparar cetonas con grupos arilo en posición γ usando precatalizadores de Pd para promover la rotura de enlaces C-C en anillos de tert-ciclobutanol utilizando cloruros de arilo y tosilatos como agentes arilantes (Capítulo 2). La transformación se caracteriza por su amplia generalidad y baja carga de catalizador. La selectividad de la reacción puede ser fácilmente controlada por la naturaleza del ligando, en la que fosfinas con grupos ricos en electrones y voluminosos dan los mejores resultados, evitando la β-eliminación de hidrógeno de las especies organometálicas intermedias. Considerando los precedentes del Capítulo 2, se ha extendido esta metodología al acoplamiento con haloacetilenos para preparar cetonas con grupos alquino en posición γ (Capítulo 3). Curiosamente, los substituyentes del grupo alquino juegan un papel fundamental en la reactividad, pudiéndose controlar mediante la utilización de un cierto ligando. En el Capítulo 4, se ha desarrollado una nueva transformación basada en una reacción catalizada por compuestos de Ni para efectuar la síntesis de anillos de ocho eslabones mediante una reacción formal de cicloadición [4+4] de benzociclobutanonas y dienos simples. Curiosamente, dicho método muestra una especial preferencia para formar anillos de ocho eslabones sobre los, a priori, anillos de 6 eslabones que son más estables termodinámicamente. En la presente tesis doctoral se ha estudiado también la viabilidad de llevar a cabo una fijación catalítica de CO2 y la formación de enlaces C-F mediante una rotura de enlaces C-C (Capítulo 5) aunque no se han encontrado las condiciones óptimas para llevar a cabo tales transformaciones.
The means to promote catalytic C-C bond-functionalization has gained a considerable attention in recent years and probably can be considered one of the most challenging and vibrant subjects in organometallic chemistry. This PhD thesis deals with the design of new metal-catalyzed functionalization of C-C bonds in four-membered ring frameworks. Specifically, we have demonstrated the viability of preparing γ-arylated ketones via Pd-catalyzed cleavage of C-C bonds in tert-cyclobutanol using aryl chloride or tosylate counterparts (Chapter 2). The transformation possesses a wide substrate scope and remarkable low catalyst loadings. Selectivity was controlled by the ligand in which electron-rich and sterically-hindered phosphine ligands provided a unique reaction outcome that avoided the proclivity of alkyl metal species towards destructive β−hydride elimination. Prompted by the precedents in Chapter 2, we successfully extended the scope of the metal-catalyzed C-C bond-cleavage of tert-cyclobutanols by using halo acetylene counterparts giving γ-alkynylated ketones (Chapter 3). Interestingly, substituents on the alkyne motif showed a remarkable influence on reactivity. Of particular interest is the application profile of such methodology since γ-alkynylated ketones could promote consecutive metal-catalyzed transformations into valuable synthetic intermediates. In Chapter 4, we extended the interest for C-C bond-cleavage beyond the use of tert-cycñobutanols. Specifically, we developed a Ni-catalyzed C-C bond-cleavage event in benzocyclobutenones for preparing eight-membered rings via formal [4+4]-cycloaddition with dienes (Chapter 4). The method shows a specific preference for eight-membered rings over thermodynamically more stable six-membered rings. This PhD thesis has also studied the development of catalytic CO2 fixation and C-F bond-formation via C-C bond-cleavage (Chapter 5). While we have not found reaction conditions to effect the desired transformations, our research group is actively involved in related catalytic endeavors and it is expected that such research will shed light into the targeted CO2 fixation or C-F bond-forming reactions via C-C bond-cleavage.
Barde, Etienne. "Catalyse au cobalt : applications en couplages croisés et en activation/fonctionnalisation de liaison C-H." Thesis, Paris Sciences et Lettres (ComUE), 2018. http://www.theses.fr/2018PSLET019.
Повний текст джерелаOrganic synthesis has been making outstanding recent progress because of the use of transition-metal catalysis into laboratory routine. Among different metals involved in catalysis, cobalt is interesting because of its low cost and toxicity but also because of its unique reactivity.During this thesis, cross-coupling and C—H bond activation reactions using cobalt complexes as catalysts were investigated.A simple catalytic system composed of diphosphine ligand and a cost-effective cobalt salt allowed us to functionnalize α-haloamides using Grignard reagents. A large variety of amides and Grignard reagents (aryl-, vinyl-, alkynyl-) were successfully tested, generating an interesting library of α-functionnalized amides.Moreover, simple cobalt salts were engaged in the activation of the C—H bond of benzamides for the aminoarylation of alkylidene cyclopropanes. Under mild conditions, original and polycyclic molecules were obtained in a single step.These results obtained in two different domains treated in this thesis demonstrate the high potential of simple cobalt salt in catalysis
Bheeter, Charles Beromeo. "Palladium-catalysed C-H bond activation for simpler access to ArSO₂R derivatives." Thesis, Rennes 1, 2013. http://www.theses.fr/2013REN1S171.
Повний текст джерелаDuring this Ph.D. period, we were interested in the C-H bonds activation catalysed by palladium catalysts for the preparation of biaryls units bearing SO₂R group. Many biological compounds present a SO₂R function and thus we chose to activate this family of substrates. This method is considered as cost effective and environmentally attractive compared to other types of couplings such as Suzuki, Stille, or Negishi. First, we demonstrated that it is possible to apply C-H bond activation method for the direct arylation of thiophene derivatives bearing a SO₂R substituent. We then established palladium-catalysed system for the selective C2 arylation of N-tosylpyrrole derivatives. We found that N-tosylpyrrole is more reactive than free NH-pyrrole. We also studied the direct arylation of heteroarenes using bromobenzenes bearing SO₂R substituents either at C2 or C4 via palladium-catalysed C-H activation. This method provides a simpler access to substituted SO₂R derivatives. Finally we developed the first palladium-catalysed dehydrogenative sp³ C-H bond functionalization/activation of N-alkyl-benzenesulfonamides to produce N-alkenyl-benzenesulfonamides. The reaction proceeds with easily accessible ligand-free Pd(OAc)₂ catalyst for aryl bromides bearing electron-withdrawing groups or PdCl(C₃H₅)(dppb) catalyst for aryl bromides with electron-donating substituents. We found that the reaction tolerates a variety of substituents both on nitrogen and on the bromobenzene moiety
Närhi, Katja. "Studies on Palladium-Catalyzed Carbocyclizations of Allene-Substituted Olefins and 1,3-Dienes." Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2006. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-794.
Повний текст джерелаLi, Haoran. "Pd-catalyzed C-H bond functionalizations of (hetero)arenes and alkenes : A one step access to poly(hetero)aromatics and styrene derivatives." Thesis, Rennes, Ecole nationale supérieure de chimie, 2020. http://www.theses.fr/2020ENCR0068.
Повний текст джерелаIn order to explain the background of my research work, in the first chapter, I summarized general mechanistic information on palladium-catalyzed C-H bond arylation and detailed some literature on direct arylation related to my research work. My objectives were to study the reactivity of new synthetic units allowing the straightforward access to bi-(hetero)aryls compounds or styrene derivatives using aryl halides or benzenesulfonyl chloride derivatives as the aryl-sources. Then, in the chapters 2-6, I summarized my research work. I studied the regiocontrolled palladium-catalyzed direct C2-arylations of Methoxsalen using benzenesulfonyl chlorides and C2,C3-diarylations using aryl bromides as the aryl sources. These results are summarized in the chapter 2. Then, I found that Pd-catalyzed direct arylation reaction allows the easy access to Ticlopidine derivatives arylated at the C5-position of the thienyl ring in one step. These results are reported in the chapter 3. In the chapter 4, we studied the reactivity of Diflufenican which contains a 1,3-difluorobenzene ring and a pyridine unit using Ru and Pd catalysis. Under appropriate conditions, two different C-H bonds of Diflufenican could be arylated. In the chapter 5, I employed different aryl sources to functionalize the C10- and C11-positions of dibenzo[b,f]azepines, and obtained asymmetric products. Through these reactions, a wide diversity of functional group were introduced on the dibenzo[b,f]azepine derivatives. Finally, in the Chapter 6, I report the first method allowing to prepare C10-arylated Cyproheptadine derivatives
Kornhaaß, Christoph Frank. "Sustainable Syntheses of Substituted Heterocycles through Ruthenium- and Palladium-Catalyzed Direct C−H Bond Functionalizations." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2014. http://hdl.handle.net/11858/00-1735-0000-0023-9911-5.
Повний текст джерелаPlaton, Mélanie. "Propriétés et performances de phosphines ferrocéniques dans le couplage C-O, C-S et C-N : nouvelles méthodologies de synthèse au palladium." Phd thesis, Université de Bourgogne, 2012. http://tel.archives-ouvertes.fr/tel-00818998.
Повний текст джерелаSofack-Kreutzer, Julien. "Synthèses de carbocycles et d'hétérocycles à cinq chaînons par activation de liaisons c(sp3)-h non activées." Phd thesis, Université Claude Bernard - Lyon I, 2011. http://tel.archives-ouvertes.fr/tel-00744243.
Повний текст джерелаHu, Yimin. "Intramolecular C-C bond formation via ruthenium and palladium catalysis : application of ruthenium catalyzed [5+2] cycloaddition for the synthesis of frondosin A and palladium catalyzed cyclizations with carbon nucleophiles /." May be available electronically:, 2007. http://proquest.umi.com/login?COPT=REJTPTU1MTUmSU5UPTAmVkVSPTI=&clientId=12498.
Повний текст джерелаGuyonnet, Mathieu. "Synthèse totale d’alcaloïdes de type dibenzopyrrocoline par arylation C(sp3)-H intramoléculaire." Thesis, Lyon 1, 2012. http://www.theses.fr/2012LYO10143.
Повний текст джерелаThe direct functionalization of unactivated C-H bonds represents an atom- and stepeconomical alternative to more traditional synthetic methods based on functional group interconversion. Transition-metal catalysis has recently emerged as a powerful tool to functionalize otherwise unreactive C-H bonds. Whereas a lot of methodological studies have been developed in the past decade, few applications of these methodologies in multi-step or total synthesis have been reported in the literature. In this context, we envisioned the total synthesis of dibenzopyrrocoline alkaloids, a family of structurally original natural products, by using intramolecular C(sp3)-H arylation as a key step. This work led us to first develop a N-arylation / bromination / intramolecular C(sp3)-H arylation sequence which allowed us to access diverse fused tricyclic indolines. We next investigated the application of this strategy to the synthesis of the dibenzopyrrocoline motif. The difficulty to access the C(sp3)-H arylation precursor required an exploration of different synthetic pathways, which proved to be potentially promising. Finally the different performed methodological studies showed the feasibility of the intramolecular C(sp3)-H arylation of tertiary anilines, which was never described in the literature
Reina, Tapia Antonio. "Metal nanoparticles stabilized by alkaloids in glycerol : from design to catalytic applications." Thesis, Toulouse 3, 2017. http://www.theses.fr/2017TOU30160.
Повний текст джерелаMetal nanoparticles (MNPs) have been largely studied in the last decades due to their interesting properties which found applications in several fields (microelectronics, materials and catalysis, among others). In contrast to common organic solvents, ionic liquids, water, supercritical CO2, polyols such as glycerol, represent innovative solvents for the immobilization of MNPs, avoiding their agglomeration and facilitating their recycling. Small, spherical, and well-dispersed Pd(0) and Ni(0) nanoparticles were synthesized under hydrogen pressure in glycerol, in the presence of different kinds of stabilizers (cinchona-based alkaloids, phosphine, polymer). The high stability of these colloidal solutions permitted the full characterization both in solution and at solid state, large-scale synthesis, and stocking the solutions for months. These colloidal catalysts were applied in a large variety of transformations including hydrogenations, hydrodehalogenations, Hiyama C-C couplings, hydrosilylation reactions, and Michael conjugate additions. Furthermore, we conducted a comparative study exhibiting the differences in catalytic reactivity by effect of the stabilizer, allowing us tuning the surface-state of the nanoparticles. Moreover, we showed the ability of glycerol to immobilize metal nanoparticles permitting the recycle of the catalytic phase between 4 and 10 times, without metal leaching. Additionally, we studied the behavior of ligand-free Ni(OAc)2 in glycerol as an alternative catalyst for C-C and C-heteroatom couplings. Also, we developped a continuous flow study, in collaboration with the Maison Européenne des Procédés Innovants (MEPI), for the hydrogenation of different functional groups, using PdNPs in glycerol
Aspin, Samuel. "Arylation migratoire C(sp3)-H d'énolates d'esters." Thesis, Lyon 1, 2013. http://www.theses.fr/2013LYO10298.
Повний текст джерелаThe transition metal catalysed functionalization of C(sp3)-H bonds unlocks numerous perspectives within organic synthesis in terms of atom economical access routes to otherwise difficult to synthesise molecules. One efficient method to exact such transformations involves the exploitation of an activated C-H bond situated adjacent to an activating electron withdrawing group, allowing facile insertion of a transition metal catalyst species and subsequent functionalization with a new species (normally an aryl group). This strategy is generally termed ‘α-functionalization’. The work detailed within this manuscript describes a diversion from the classic, and well documented α-functionalization reaction, in which rearrangement steps within the catalytic cycle give rise to β- and more remote substrate functionalization. The first new methodology to be described involves a fundamental extension to the in-house developed β-arylation reaction, in which, through careful substrate and ligand choice, this methodology could be applied to achieve the functionalization of simple ester enolates in remote γ- to η - positions. The developed strategy allowed the synthesis of a small range of interesting homophenylalanine analogues, and higher homologues. The second methodology to be described involves a necessary modified protocol for the β-arylation reaction, in which silyl ketene acetals were exploited as mild metal-enolate surrogates, allowing the coupling of base-sensitive substrates. The previously described reaction scope has been extended in terms of both the electrophile and nucleophile coupling partners through the development of mild reaction conditions, which subsequently allowed application of several products towards the synthesis of lactones
Biosca, Brull Maria. "Fitting the catalysts for effective enantioselective C-X bond forming reactions. Theoretically guided ligand design and mechanistic investigations." Doctoral thesis, Universitat Rovira i Virgili, 2018. http://hdl.handle.net/10803/665121.
Повний текст джерелаLa creciente demanda de compuestos enantioméricamente puros, ha incrementado el interés por el desarrollo de metodologías para la obtención de dichos compuestos. Entre ellas, la catálisis asimétrica es la técnica mas utilizada. En dicha metodología, la elección del ligando quiral es clave para la obtención de elevada actividades i enantioselectividades. En este contexto, esta tesis se centra en la síntesis de diferentes familias de ligandos quirales altamente modulares a partir de productos de partida de elevada disponibilidad. Más concretamente, se ha trabajado en la síntesis de ligandos heterodadores P-oxazoline (P= fosfina, fosfinito, fosfito, fosforamidito), P-otros grupos N-dadores (P= fosfito, fosforamidito, fosfonito y N= tiazol, sulfoximina, hidrazona, amina, piridina), P-tioéter (P= fosfina, fosfinito, fosfito) i una familia de ligandos fosfina quiral-fosfito. Estos ligandos se han aplicado en la reacción de hidrogenación de olefinas funcionalitzadas i mínimamente funcionalitzadas catalizada por Rh i Ir, la reacción de substitución alílica y la reacción de protonación descarboxilativa de oxindolas ambas catalizadas por Pd. Además, en algunos casos, se han realizado cálculos computacionales en combinación con ensayos experimentales para estudiar el origen de las enantioselectividades obtenidas o bien para guiar la optimización de los ligandos.
The growing demand on enantiomerically pure compounds has stimulated the interest for the development of methodologies to obtain these compounds. Among them, asymmetric catalysis is one of the most employed tools. In this technic, the choice of the chiral ligand is fundamental to obtain high levels of activity and enantioselectivity. In this context, this thesis is focused on the synthesis of several families of highly modular chiral ligands from readily available starting materials. Particularly, we worked on the synthesis of P-oxazoline (P= phosphine, phosphinite, phosphite, phosphoroamidite), P-other N-donor groups (P= phosphite, phosphoroamidite, phosphonite and N= thiazole, sulfoximine, hydrazone, amine, pyridine), P-thioether (P= phosphine, phosphinite, phosphite) and a family of P*-stereogenic phosphine-phosphite ligands. These ligands have been applied in the Rh- and Ir-catalyzed hydrogenation of functionalized and minimally functionalized olefins, Pd-catalyzed allylic substitution reaction and Pd-catalyzed decarboxylative protonation. Furthermore, in some cases, DFT studies in combination with experimental ones have been performed to better understand the origin of the obtained enantioselectivities or in order to guide the ligand optimization.
Rovira, Coll Mireia. "Reaction mechanisms involved in cross coupling processes catalysed by copper and nickel." Doctoral thesis, Universitat de Girona, 2017. http://hdl.handle.net/10803/403434.
Повний текст джерелаLes espècies aril-CuIII han estat proposades com les espècies a través de les quals operen els acoblaments tipus Ullmann. No obstant, aquestes espècies són molt reactives i difícilment detectables en els processos fonamentals que governen aquests acoblaments. La primera part d’aquesta tesi es centra en l’estudi de la reactivitat de complexes ben definits aril-CuIII davant de metilens actius (Reacció de Hurtley) i acetilens terminals (Reacció de Stepens-Castro). La següent part es centra en la síntesi i caracterització de complexes ben definits aril-NiII, anàlegs als de coure. La curta distància de l’enllaç Ni-C dissenteix la seva reactivitat davant diversos nucleòfils via eliminació reductiva. Per contra, aquestes espècies són reactives en presència de fonts electrofíliques de CF3+. En l’última part, ens centrem en l’estudi de les propietats estèriques dels lligands auxiliars coordinats al centre de coure i la selectivitat que presenten envers diferents nucleòfils en els sistemes estàndards de tipus Ullmann
Margalef, Pallarès Jèssica. "Screening of modular and readily available ligand libraries for C-X (X=H, C, N and O) bond forming reactions. The use of DFT studies for catalysts optimization." Doctoral thesis, Universitat Rovira i Virgili, 2016. http://hdl.handle.net/10803/386578.
Повний текст джерелаEl creciente interés para la obtención de compuestos enantioméricamente puros para la obtención de compuestos enantioméricamente puros, ha conducido a un importante desarrollo de la catálisis asimétrica. En este contexto, esta tesis se centra en la síntesis de varias familias de ligandos quirales altamente modulares a partir de compuestos de fácil disponibilidad. Concretamente, se ha trabajado en la síntesis de ligandos fosfito-tioéter, fosfito-piridina, fosfito-triazoles y ligandos hidroaximida y tioamida. Todos ellos tienen en común que son sólidos, estables y por lo tanto de fácil manipulación. Estos ligandos se han aplicado en la hidrogenación de olefinas funcionalizadas y no funcionalizadas catalizada por Rh e Ir, en la reducción de cetonas mediante transferencia de hidrógeno catalizada por Rh y Ru, en reacciones de sustitución alílica catalizada por Pd y en el adición de organoaluminiatos a aldehídos catalizada por Ni. Además, en algunos casos se han realizado estudios DFT para agilizar el proceso de optimización de los ligandos. Así pues, se ha logrado la obtención de diferentes compuestos químicos quirales de alto interés sintético (ej. alcoholes, alcanos funcionalizados y no funcionalizados, alilos sustituidos) en grandes enantioselectividades y en el mejor de los casos se han conseguido los productos en su forma enantioméricamente pura (> 99% ee).
The growing interest in obtaining enantiomerically pure compounds in obtaining enantiomerically pure compounds has led to a significant development in the field of asymmetric catalysis. In this context, this thesis is focused on the synthesis of several families of highly modular chiral ligands from readily available compounds. Specifically, we worked on the synthesis of thioether-phosphite ligands, phosphite-pyridine, phosphite-triazole and hidroaximide and thioamide ligands. They all have in common that are solid, stable and therefore easy to handle. These ligands have been applied in the Rh- and Ir-catalyzed hydrogenation of functionalized and unfunctionalized olefins, in the Ru- and Rh-catalyzed asymmetric transfer hydrogenation of ketones, in Pd-catalyzed allylic substitution reactions and in the Ni-catalyzed addition of organoalumininum to aldehydes. Moreover, in some cases DFT studies have been performed to speed up the optimization of ligands. Hence, a variety of chiral chemical compounds of high synthetic interest (i. e. alcohols, functionalized and non-functionalized alkanes, substituted allyl) lhigh enantioselectivities were achieved and in some cases the products were obtained in their enantiomerically pure form(> 99% ee).