Дисертації з теми "Arylation Reactions"
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Sävmarker, Jonas. "Palladium-Catalyzed Carbonylation and Arylation Reactions." Doctoral thesis, Uppsala universitet, Avdelningen för organisk farmaceutisk kemi, 2012. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-167720.
Повний текст джерелаDouglas, Gayle Elizabeth. "Investigations into direct N-arylation reactions." Thesis, University of Leeds, 2018. http://etheses.whiterose.ac.uk/23026/.
Повний текст джерелаLafrance, Marc. "Development of new palladium-catalyzed arylation reactions." E-theses uOttawa (Restricted to University of Ottawa), 2008. https://login.proxy.bib.uottawa.ca/login?url=http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqdiss&rft_dat=xri:pqdiss:NR41635.
Повний текст джерелаFujino, Daishi. "Studies on Palladium-Catalyzed Arylative Cyclization Reactions." 京都大学 (Kyoto University), 2014. http://hdl.handle.net/2433/188508.
Повний текст джерелаLjungkvist, Oskar. "Mechanochemistry : C-H arylation and annulative π-extension reactions attempted inball mill". Thesis, Uppsala universitet, Institutionen för kemi - BMC, 2018. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-382088.
Повний текст джерелаSambiagio, Carlo. "Investigations on the use of amidic ligands in copper-catalysed arylation reactions." Thesis, University of Leeds, 2015. http://etheses.whiterose.ac.uk/10153/.
Повний текст джерелаTanji, Yutaka. "Steric Effect of Carboxylate Ligands on Pd-Catalyzed C-H Bond Arylation Reactions." Kyoto University, 2020. http://hdl.handle.net/2433/253293.
Повний текст джерелаSundalam, Sunil Kumar. "The Discovery and Development of Metal-Free Arylation Reactions with Unsymmetrical Diaryliodonium Salts." PDXScholar, 2017. https://pdxscholar.library.pdx.edu/open_access_etds/3764.
Повний текст джерелаSchroll, Peter [Verfasser], and Burkhard [Akademischer Betreuer] König. "Photocatalytic single-electron transfer reactions: the Photo-Meerwein arylation / Peter Schroll. Betreuer: Burkhard König." Regensburg : Universitätsbibliothek Regensburg, 2016. http://d-nb.info/1096750597/34.
Повний текст джерелаCooke, Michael Liam. "Development of novel arylation and alkenylation reactions using hypervalent iodine reagents and copper catalysis." Thesis, University of Cambridge, 2011. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.609862.
Повний текст джерелаAoki, Yuma. "Development of Iron-Catalyzed C-N and C-C Bond Forming Reactions toward Functional Arylamine Synthesis." Kyoto University, 2019. http://hdl.handle.net/2433/242518.
Повний текст джерелаPérez, Janer Ferran. "Palladium in azaheterocyclic synthesis: α-arylation of sulfones, domino processes and C-H carbene insertion reactions". Doctoral thesis, Universitat de Barcelona, 2018. http://hdl.handle.net/10803/586010.
Повний текст джерелаDe entre todos los metales de transición utilizados en síntesis orgánica, el paladio ha ocupado un lugar central durante décadas y ha sido uno de los metales que más ha contribuido al desarrollo de este campo. En la presente Tesis Doctoral se han desarrollado diversas metodologías para la síntesis de heterociclos nitrogenados basados en procesos dominó catalizados por paladio. Por otro lado, los estudios experimentales se han combinado con estudios computacionales DFT para desentrañar el mecanismo implicado en estas transformaciones. En la primera parte de la Tesis Doctoral se ha llevado a cabo un extenso estudio de la reacción de α-arilación intramolecular de sulfonas catalizado por paladio. La combinación de la reacción de α-arilación con la subsiguiente adición conjugada a diversos aceptores de Michael, ha permitido el desarrollo de procesos dominó en 2, 3 y 4 etapas para la síntesis de tetrahidroisoquinolinas e indoles diversamente funcionalizados. Los estudios computacionales DFT de este proceso para la formación de indoles sugieren que la reacción de α-arilación transcurre mediante un proceso de desprotonación-metalación concertado (CMD) seguido de una eliminación reductora. H SO2R' SO2R' Pd(0) I base SO2R' SO2R' PhO2S SO2R' n= 0,1 N n Aza-Michael N -arilación N n n adición N R conjugada n=1 SO2R' SO2R' adición conjugada n=0 R'O2S SO2R' N -eliminación N R R A continuación, la reacción de α-arilación intramolecular catalizada por paladio se ha extendido a la utilización de sulfonatos, sulfonamidas y fosfonatos. Aunque los tres tipos de nucleófilos pueden utilizarse en la reacción de α-arilación para la preparación de tetrahidroisoquinolinas, la reacción transcurre de manera menos eficiente en relación a las sulfonas estudiadas. Asimismo, la versatilidad de los procesos dominó desarrollados a partir de ésteres sulfónicos y sulfonamidas fue menor. Por otro lado, los fosfonatos han resultado ser completamente inactivos en los diferentes procesos domino estudiados. La reacción de α-arilación de sulfonatos, sulfonamidas y ésteres sulfónicos también se ha estudiado computacionalmente. Estos estudios han puesto de manifiesto que la reacción transcurre por mecanismos distintos en función del nucleófilo y de la base utilizada. En la segunda parte de la Tesis, se ha estudiado la viabilidad de los complejos de paladio en reacciones de inserción de carbenos en enlaces C-H generados a partir de α-diazoacetamidas. La descomposición de las α-diazo-α-(metoxicarbonil) acetanilidas catalizadas por complejos de paladio ha dado lugar a la formación de oxindoles como resultado de una inserción quimioselectiva en el enlace Csp2-H. Aunque tanto los catalizadores de Pd(0) como los de Pd(II) pueden promover esta reacción de inserción, los mejores resultados se han obtenido al utilizar complejos de Pd(0), en especial Pd2(dba)3 o [(IMes)Pd(NQ)]2. Los cálculos computacionales DFT de este proceso sugieren que la inserción tiene lugar mediante un mecanismo por etapas inédito que implica una migración 1,5 de hidrógeno promovida por el paladio seguido de un proceso de eliminación reductora. Finalmente, también se ha estudiado la descomposición de α-diazo-α- (metoxicarbonil) acetamidas catalizada por paladio para promover inserciones Csp3-H y la formación de β-lactamas. Aunque tanto los catalizadores de Pd(0) como de Pd(II) son capaces de promover esta reacción, los catalizadores de Pd(II) son más eficientes y versátiles.
Phipps, Robert James. "Copper catalysis as a tool for developing novel and selective arylation reactions using hypervalent iodine reagents." Thesis, University of Cambridge, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.608863.
Повний текст джерелаOvadia, Benjamin. "Nouvelles réactions radicalaires multicomposants : carbo-arylation, carbo-oximation, carbo-alcénylation d'oléfines." Thesis, Bordeaux, 2014. http://www.theses.fr/2014BORD0451/document.
Повний текст джерелаThis thesis consists in the development of new sulfonylated acceptors for the elaboration of original free-radical multicomponent processes. Thereby, we have developed new free-radical carbo-arylation, carbo-oximation and carbo-alkenylation processes onto olefins.We have first studied the feasibility of new free-radical carbo-heteroarylation based on two different way of activation. This process proved to be very challenging due to the mismatch polarity between the different components, leading to the formation of side reactions and therefore relatively poor yield.In a second part, we examined the diastereocontrol arising from carbo-oximation of chiral allylsilanes and allylic esters. Carbo-oximation products are obtained with high level of selectivity, albeit in modest yields, due to steric hindrance and the formation of side-products. The relative configuration of the major diastereoisomer could not be established, but transition state models may be proposed to predict the most favorable stereochemistry. In order to overcome the use of stoechiometric amount of tin, we have developed new bi-functional reagents which can act both as a trap for nucleophilic radicals as well as a source of electrophilic radical via α-scission of generated alkylsulfonyl radicals. We have developed a very simple and efficient method for the preparation of these acceptors allowing an access to a wide range of compounds.In the final part, we extended the results obtained in the carbo-alkenylation reactions by preparing new activated halogenated and sulfonylated acceptors containing electron-withdrawing groups. We finally carried out a successful test on a carbo-alkenylation reaction using a vinylsulfoxide, offering an entry toward the development of such reactions in an enantioselective series starting from enantioenriched vinylsulfoxides
Tomohara, Keisuke. "New aspects in chemistry of axially chiral enolates: Developments of asymmetric reactions via C-O axially chiral enolates and α-arylation of amino acids derivatives". 京都大学 (Kyoto University), 2012. http://hdl.handle.net/2433/157896.
Повний текст джерелаBassoude, 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.
Повний текст джерелаNaas, Mohammed. "Synthèse et fonctionnalisation de nouveaux dérivés d’indazoles à visée thérapeutique." Thesis, Orléans, 2016. http://www.theses.fr/2016ORLE2009/document.
Повний текст джерелаAccess to new biologically active compounds requires the development of new rapid and efficient methods for the synthesis of original heterocyclic scaffolds. In this context, we decided to focus particularly on the reactivity of indazoles. First, we studied the selectivity of Suzuki cross-coupling reaction to functionalize position 3 of the indazole with the free NH function. Indeed, we have described the first example of the direct and regioselective palladium-catalyzed (hetero)arylation of indazoles, the reaction may be induced to occur at either in position 3 and 7. We then showed the possibility of "one-pot" synthesis of disubstituted indazolic entities. Moreover, in order to increase diversity around the indazole scaffold, we developed a direct and regioselective alkenylation of (2H)- and (1H)-indazoles by oxidative palladium catalyzed at the C-3 and C-7, then we envisaged a three staps synthesis of Gamendazole, molecule currently in clinical phase for male contraception, by using the direct alkenylation at C3 of the suitably functionalized (1H)-indazoles. The last part of this report was dedicated to the preparation of indazoles containing a sulphonamide function, with the aim of biological testing them as potentially anti-cancer candidates
Naturale, Guillaume. "Approches radicalaires pour la fonctionnalisation directe de quinones à visée anticancereuse." Thesis, Bordeaux 1, 2012. http://www.theses.fr/2012BOR14635/document.
Повний текст джерелаIn our ongoing course dedicated to the discovery of small anticancer molecules, we designed novel quinone derivatives. Our first objective was to fashion non-peptidic Smac mimics, able to trigger apoptosis in tumor cells, displaying a structure rigidified by conformational restrictions. Otherwise, the kinases and the phosphatases, acting as phosphorylating / dephosphorylating agents mostly in the control of the cell cycle, were thought to be other relevant biological targets. An intent study of their known inhibitors allowed us to underline trends in their chemical structure and made us plan the synthesis of functionalized naphthoquinones.A dedicated approach involving radical decarboxylation of amino acids allowed the introduction of aliphatic side chains on our substrates though C(sp2)–C(sp3) bond formation. Ag(I)/S2O82- was used as alkyl radical initiator and the direct C-H alkylation of the quinonic positions could take place. C(sp2)–C(sp2) bonds were created through aryl radicals generation from stable diazonium salts or anilines which allowed the direct C-H arylation of quinones. The procedures described along this manuscript let us formulate several advances on the substrates reactivity and on the reaction mechanisms involved
Corrie, Thomas James Alexander. "Intramolecular direct arylation." Thesis, University of Edinburgh, 2017. http://hdl.handle.net/1842/28820.
Повний текст джерелаZine, Khalid. "Synthèse régio- et stéréosélective du 4,4,4-trifluorobut-2-énoate d'éthyle porteur d'un groupement tributylstannyl en position alpha ou bêta : réactivité cupro-catalysée des vinylétains en l'absence de complexes du palladium." Thesis, Tours, 2011. http://www.theses.fr/2011TOUR4044/document.
Повний текст джерелаThe development of a simple method to obtain perfluoroalkylated building blocks for their subsequent utilization in the synthesis of Rf-containing compounds is therefore essential to organofluorine chemistry. Perfluoroalkylated vinyl metals constitute an important class of these building blocks.In order to prepare a new perfluoroalkylated bulding blocks, we investigated transition metal-catalyzed-free hydrostannylation of ethyl 4,4,4-trifluorobut-2-ynoate 1. The hydrostannylation took place smoothly in the absence of additive, providing regioselectively high yields of the corresponding α or β stannylated alkenoates depending on the nature of the solvent used. Indeed, we have demonstrated that the hydrostannylation of 1 in hexane provided the β-stannylated product with high regioselectivity (>95%) and excellent yield (>97%). Using methanol as solvent, total α-regioselectivity of the hydrostannylation of 1 was observed, providing α -tributylstannylacrylate as the sole regioisomer in a nearly quantitative yield.Theses new vinyltins reagents readily undergo copper (I) catalyst coupling reactions with various electrophiles as allyl, propargyl, benzyl and alkynyl bromides to provide good yields of the new corresponding acrylates esters bearing a β-trifluoromethyl group.This method provided a new efficient entry to this important class of compounds
Skhiri, Aymen. "Réactivité des chlorures de benzènesulfonyle pour l'accès à des hétéroarènes et alcènes arylés via des réactions pallado-catalysées." Thesis, Rennes 1, 2017. http://www.theses.fr/2017REN1S080.
Повний текст джерелаIn this thesis we have been interested in the synthesis of arylated heterocycles via the activation of sp2 C-H bonds of heteroaromatics and to the synthesis of halo-substituted arylated alkenes using palladium-catalysis. The products obtained are considered to be molecular bricks which are of interest to biochemists as well as to the preparation of materials. The catalyst system Pd(MeCN)2Cl2/Li2CO3/dioxane allows the direct access to a wide variety of arylated molecules from heteroarenes or alkenes and benzenesulfonyl chlorides. We have developed a method for the direct β-arylation of selenophenes from selenophenes and benzenesulfonyl chlorides. We have also shown that the use of (poly)halogenated benzenesulfonyl chlorides makes it possible to synthesize, by Pd-catalyzed reactions, (poly)halo-substituted arylated heteroarenes, stilbenes or cinnamates
Grosse, Sandrine. "Imidazo[1, 2-b]pyrazoles, imidazo[1, 2-a]imidazoles : synthèse, fonctionnalisation et évaluation biologique." Thesis, Orléans, 2013. http://www.theses.fr/2013ORLE2056.
Повний текст джерелаImidazo[1,2-b]pyrazoles and imidazo[1,2-a]imidazoles are entities with some interesting applications in pharmacology. However, despite this potential, few methods of preparation and direct functionalisation of the heterocyclic moiety have been described. In this context, the overall goal of our research is to develop new routes to these bicyclic systems from readily available starting materials. Strategies of functionalisation of the heterocyclic moiety were then explored in order to design diversified libraries for the evaluation of potential biological activities. Herein, the results of the tests of imidazo[1,2-b]pyrazole series against various cancer lines are reported
Seo, Sangwon. "Decarboxylative and direct functionalisations of aromatic compounds." Thesis, University of Manchester, 2014. https://www.research.manchester.ac.uk/portal/en/theses/decarboxylative-and-direct-functionalisations-of-aromatic-compounds(a9ddab1b-86a0-491e-a95b-d6b40c8bd7ab).html.
Повний текст джерелаBielawski, Marcin. "Diaryliodonium Salts : Development of Synthetic Methodologies and α-Arylation of Enolates". Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2011. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-54738.
Повний текст джерелаFelipe-Blanco, Diego. "Salicylic Acid-Catalyzed Radical Arylations from In-situ Formed Arenediazonium Salts." Doctoral thesis, Universidad de Alicante, 2020. http://hdl.handle.net/10045/112757.
Повний текст джерелаGonçalves, Renato Sonchini [UNESP]. "Síntese e caracterização de amino ácidos e ésteres n-(aminoalquil)-lactâmicos derivados do paba com potencial atividade biológica." Universidade Estadual Paulista (UNESP), 2010. http://hdl.handle.net/11449/99656.
Повний текст джерелаConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
Amino ésteres lactâmicos derivados do PABA e que podem ser potencialmente bioativos, por exemplo, como anestésicos locais, foram sintetizados com bons rendimentos por uma reação seletiva de SnAr de ácidos benzóicos com n-(3-aminopropil)-lactamas seguida por esterificação com aminoálcoois terciários. Produtos da N-arilação do N, N-dimetilformamida foram também obtidos através da esterificação direta do ácido 4-cloro-3-nitrobenzóico
Lactamic amino esters PABA-related, and can potentially bioactive, for exemple, as local anesthetics were synthesized in good yields by a selective 'S IND. n'Ar reactions of benzoic acids with N-(3-aminopropyl)lactams followed by esteterification with tertiary aminoalcohols. Products of the N-arylation with N,N-dimethylformamide are also obtained through of direct esterification of 4-chloro3-nitrobenzoic acid
Gonçalves, Renato Sonchini. "Síntese e caracterização de amino ácidos e ésteres n-(aminoalquil)-lactâmicos derivados do paba com potencial atividade biológica /." Bauru : [s.n.], 2010. http://hdl.handle.net/11449/99656.
Повний текст джерелаBanca: Alvicler Magalhães
Banca: Wanda Pereira Almeida
O Programa de Pós-Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi da Unesp
Resumo: Amino ésteres lactâmicos derivados do PABA e que podem ser potencialmente bioativos, por exemplo, como anestésicos locais, foram sintetizados com bons rendimentos por uma reação seletiva de SnAr de ácidos benzóicos com n-(3-aminopropil)-lactamas seguida por esterificação com aminoálcoois terciários. Produtos da N-arilação do N, N-dimetilformamida foram também obtidos através da esterificação direta do ácido 4-cloro-3-nitrobenzóico
Abstract: Lactamic amino esters PABA-related, and can potentially bioactive, for exemple, as local anesthetics were synthesized in good yields by a selective 'S IND. n'Ar reactions of benzoic acids with N-(3-aminopropyl)lactams followed by esteterification with tertiary aminoalcohols. Products of the N-arylation with N,N-dimethylformamide are also obtained through of direct esterification of 4-chloro3-nitrobenzoic acid
Mestre
Dell'Acqua, M. "NEW SYNTHETIC STRATEGIES FOR THE PREPARATION OF HETEROCYCLIC AND HETEROPOLYCYCLIC COMPOUNDS." Doctoral thesis, Università degli Studi di Milano, 2012. http://hdl.handle.net/2434/170500.
Повний текст джерелаBenhaddou, Rachida. "Arylation de doubles liaisons catalyses par le palladium : influence de differents facteurs sur la cinetique de la reaction, etude de nouvelles syntheses d'aryl-c-glycosides." Paris 6, 1988. http://www.theses.fr/1988PA066065.
Повний текст джерелаZhang, Yin. "Backbone decoration of imidazol-2-ylidene ligands with amino groups and their application in palladium catalyzed arylative amination reaction." Thesis, Toulouse 3, 2015. http://www.theses.fr/2015TOU30109/document.
Повний текст джерелаThis work is incorporated within the framework of the chemistry of N-Heterocyclic Carbenes (NHCs) and aims at functionalizing the skeleton of imidazol-2-ylidenes by attachment of one or two amino groups. Two new NHC classes were first obtained by this strategy, namely the 4-(dimethylamino)imidazol-2-ylidene IArNMe2 and the 4,5-bis(dimethylamino)imidazol-2-ylidene IAr(NMe2)2. The synthesis of the precursors of these NHCs, the 4-(dimethylamino)imidazolium triflates (IArNMe2)·HOTf and the 4,5-bis(dimethylamino)imidazolium triflates (IAr(NMe2)2)·HOTf is based on the coupling between the corresponding disubstituted formamidine and either an a-chloroacetamide for the mono-amino derivative or a reactive dichlorodiaminoethene for the bis-amino analogue. The electronic properties of the resulting new NHCs ligands have been studied by measurement of their Tolman Electronic Parameter (TEP) values obtained from the IR spectra of the complexes [Rh(IMesXY)Cl(CO)2] and by 77Se NMR spectroscopy of their corresponding selenoureas [(IMesXY)=Se]. It was shown that the electronic donation of the carbenic carbon sequentially increases by decoration with one or two amino groups respectively whereas the p-accepting properties of the NHC are only slightly or even not affected by the adjunction of the NMe2 groups on the imidazolyl backbone. Later, the synthesis of the two new PEPPSI-type palladium pre-catalysts PEPPSI-Pd-IPrNMe2 and Pd-PEPPSI-IPr(NMe2)2 were successfully achieved. From the calculated the percent buried volume %Vbur which is related to the steric properties of the two supporting NHC ligands, it appeared that grafting one amino group onto the backbone already leads to significant improvement of steric congestion while the second amino only results in a slight increase of the steric issue. The catalytic efficiencies of both pre-catalysts were evaluated in the benchmark Buchwald-Hartwig amination and compared with this of the reference PEPPSI-Pd-IPr. The bis-aminated pre-catalyst Pd-PEPPSI-IPr(NMe2)2 was shown to be the most active and stable pre-catalyst, and it was shown to be also highly efficient in more challenging amination reaction. It indeed allows to carry out the amination of aryl chlorides at low catalyst loadings or by using a mild base such as cesium carbonate, and even to activate the aryl tosylates, which are more difficult substrates than aryl chlorides. In order to study the critical stereoelectronic properties of the NHC ligands for the efficiency of the corresponding catalysts, further derivatization of the heterocyclic backbone was carried out, either by increasing the bulkiness of the mono-amino group from dimethylamino to diisopropylamino group to generate the carbene IArNiPr2, or by formally replacing one dimethylamino group by an halogen X in the bis-aminoimidazo-2-ylidene to give the carbenes IArNMe2,X. While the imidazolium salts (IArNiPr2)·HOTf was synthesized following the same method as (IArNMe2)·HOTf, the oxidative halogenation of the backbone of (IArNMe2)·HOTf with a N-halosuccinimide afforded (IArNMe2,X)·HOTf in good yields under very mild conditions. Noteworthy, this original reactivity was also observed on the rhodium and palladium complexes of this ligand
Medley, Jonathan William. "Direct dehydrative N-Pyridinylation of amides, the interrupted Bischler-Napieralski reaction, and the enantioselective total synthesis and arylative dimerization of aspidosperma alkaloids." Thesis, Massachusetts Institute of Technology, 2013. http://hdl.handle.net/1721.1/82319.
Повний текст джерелаCataloged from PDF version of thesis. Vita.
Includes bibliographical references.
I. Direct Dehydrative N-Pyridinylation of Amides A method for the single-step N-pyridinylation of secondary amides is described. The process involves electrophilic activation of secondary amides with trifluoromethanesulfonic anhydride in the presence of 2-fluoropyridine followed by introduction of a pyridine N-oxide derivative and warming to afford the corresponding N-pyridinyl tertiary amide derivatives. The structure of activated amide intermediates is probed through in situ monitoring, and a mechanism supported by in situ monitoring and deuterium labeling experiments is discussed. II. Synthesis of Spirocyclic Indolines by Interruption of the Bischler-Napieralski Reaction The development of a versatile method for the synthesis of spirocyclic pyrrolidinoindolines is described. Treatment of N-acyltryptamines with trifluoromethanesulfonic anhydride-2-chloropyridine reagent combination affords highly persistent spiroindoleninium ions, which are selectively trapped intra- and intermolecularly by various nucleophiles. III. A Concise and Versatile Double-Cyclization Strategy for the Highly Stereoselective Synthesis and Novel Arylative Dimerization of Aspidosperma Alkaloids A strategy for the concise, stereoselective synthesis of aspidosperma alkaloids and related structures via a common putative diiminium ion intermediate is described. The approach enables the dimerization of aspidosperma-type structures at the sterically hindered C2-position. The diiminium intermediate is prepared in situ from an enantioenriched [alpha]-quaternary 2- chlorotryptamine lactam through a stereoselective electrophilic double-cyclization cascade. The key C5-quaternary stereocenter is secured via successive diastereoselective [alpha]-alkylations of pseudoephenamine crotonamide.
by Jonathan William Medley.
Ph.D.in Organic Chemistry
Tomakinian, Terry. "Nouvelles méthodes de synthèse de benzofuroindolines. Vers la synthèse de la phalarine." Thesis, Université Paris-Saclay (ComUE), 2015. http://www.theses.fr/2015SACLS031.
Повний текст джерелаBenzofuroindolines are a family of compounds which can be found in two regioisomeric forms: benzofuro[2,3-b]indolines or benzofuro[3,2-b]indolines. This core is present in several natural products such as bipleiophylline, voacalgine A, diazonamide A or phalarine which have been the subject of intensive efforts towards their syntheses. The postulated biogenesis is the oxidative coupling of an indole and a phenol. We developed four pathways to access these structures using the indole nucleus.The first part consisted in a direct oxidative coupling between a N-acetylindole and a phenol in presence of FeCl₃ and DDQ. This strategy showed its generality on N-acetylindoles derivatives to form in only one step the benzofuro[3,2-b]indoline core. In some cases, the benzofuro[2,3-b]indoline is obtained if the substitution in the C-2 and C-3 position is the same. In order to synthesize the phalarine, the unique natural product to possess a benzofuro[3,2-b]indoline core, we designed a C-2 arylation of an indole with a phenol using a palladium-catalyzed coupling. The cyclization steps using NIS led to the benzofuro[3,2-b]indoline core. The insertion of the missing carbon of one of the rings is under study by adding a nucleophile which contains only one carbon and a leaving group. The last strategy to access to benzofuro[3,2-b]indolines has been focused on an interrupted Fischer indolization. The reaction between benzofuran-3-ones and arylhydrazines in acidic conditions led to the desired benzofuro[3,2-b]indolines. This methodology is general and robust. Another part of the project was to achieve the Umpolung of the indole to add nucleophiles in C-3 position of the indole nucleus. N-hydroxyindoles were synthesized and the use of biaryliodonium triflate salts allowed an O-arylation reaction. The product being unstable, a [3,3] sigmatropic rearrangement can take place to afford the desired benzofuro[2,3-b]indolines
Alsalim, Rana. "Contribution à la synthèse totale de la céphalotaxine." Thesis, Paris 11, 2013. http://www.theses.fr/2013PA114811/document.
Повний текст джерелаFor more than 40 years the chemists were interested in the extraction, in the biological activity and in the synthesis of the homoharringtonine, a natural ester of cephalotaxine, which is a powerful antileukemic compound of therapeutic use, in particular against the leukaemia resistant to tyrosine kinase inhibitors. These alkaloids are extracted from Cephalotaxus, conifers native of the South of China with extremely slow growth. The objective of this work thus consisted in developing a concise synthesis of the cephalotaxine, to limit the recourse to the endangered vegetable resource The developed strategy requires an intermolecular Heck-coupling of electronically and sterically deactivated demanding substrates. The preliminary results having been disappointing, the first objective consisted in developing the use of the model of the experimental design in total synthesis because the classic methodology of variation of a single parameter at the same time said of "one by one" was ineffective. The application of a complete factorial design overcomes this problem by a model study, allowing to determine the optimized parameters to make this coupling reaction effective. We then synthesized the precursors from naturally abundant safrol and 2,3-butanedione then realized the Heck coupling with the aim of the access to the precursor AC containing all the atoms of carbon of cephalotaxine and the features required for its later cyclization in pyrrolobenzazepine ABC fragment. The o-iodized homopiperonylic alcohol led in certain conditions to an isochromane through a tandem Heck-oxa-Michael reaction. Finally, we have functionalized the Heck and hydro-arylation products obtained with 69-70 % yield in position C3 by different methods allowing us to validate our strategy to access these alkaloids
Trejos, Alejandro. "Palladium-Catalysed Couplings in Organic Synthesis : Exploring Catalyst-Presenting Strategies and Medicinal Chemistry Applications." Doctoral thesis, Uppsala universitet, Avdelningen för organisk farmaceutisk kemi, 2012. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-173068.
Повний текст джерелаThe time 12:05 for the public defense mentioned in the thesis is incorrect. It will take place at 09:15, 2012-06-08.
Sarnpitak, Pakornwit. "Scaffold-oriented Synthesis for Drug Discovery." Thesis, Griffith University, 2017. http://hdl.handle.net/10072/366103.
Повний текст джерелаThesis (PhD Doctorate)
Doctor of Philosophy (PhD)
School of Natural Sciences
Science, Environment, Engineering and Technology
Full Text
Eichhorst, Christoph. "Untersuchungen zur Synthese fluoreszenzaktiver aromatischer Polyzyklen durch Palladium-katalysierte Domino-C‒H-Aktivierungen." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2014. http://hdl.handle.net/11858/00-1735-0000-0023-993C-7.
Повний текст джерелаEriksson, Ludvig. "Transition Metal Mediated Transformations of Carboranes." Doctoral thesis, Uppsala University, Organic Chemistry, 2003. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-3324.
Повний текст джерелаThis thesis describes the use of copper and palladium to mediate transformations of carboranes, especially p-carborane.
1-(1-p-carboranyl)-N-methyl-N-(2-butyl)-3-isoquinolinecarboxamide, a carborane containing analogue of the peripheral benzodiazepine receptor (PBR) ligand PK11195, has been synthesised. A key step in the reaction is the copper (I) mediated coupling of p-carborane with ethyl 1-bromo-isoquinoline-3-carboxylate.
p-Carborane has been arylated on the 2-B-atom in high yields, using the Suzuki–Miyaura reaction. Thus the reaction between 2-I-p-carborane and various arylboronic acids [1-naphthyl-, phenyl-, 4-MeO-C6H4-, 3-CH3CONH-C6H4-, 4-NC-C6H4-, 3-NO2-C6H4-], gave the corresponding 2-aryl-p-carboranes in DME solution when reacted in the presence of cesium fluoride and the catalytic Pd2(dba)3–dppb system. Under the same conditions, the boron-boron bond forming reaction of two p-carboranylboronic esters (2-[(pinacolato)boron]-p-carborane and 2-[(neopentyl glycolato)boron]-p-carborane) was also shown feasible.
p-Carborane has been vinylated on the 2-B-atom in high yields by use of the Heck reaction. The coupling between 2-I-p-carborane and various styrenes [4-H-, 4-C6H4-, 4-Cl , 4-Br-, 4-NO2-, 4-CH3O- and 4 CH3 ] resulted in the formation of the correspondingtrans-β-(2-B-p-carboranyl) styrene in DMF solution when reacted in the presence of silver phosphate and the palladacycle Herrmann´s catalyst. The reaction was shown to proceed at higher rate with electron rich than with electron deficient olefins.
The feasibility of palladium-catalysed isotopic exchange of an iodinated closo-carborane with a radioisotope of iodine has been studied. 2-I-p-carborane was selected as a model compound. It was shown, that such isotopic exchange is possible and provides a high yield (83 ± 4.2 %) during 40 min long reaction. The reaction conditions were optimised, and it was demonstrated that presence of the tetra n-butylammonium hydrogensulphate is important in order to stabilise catalyst and provide reproducibility of labelling. In this work we have modified the methodology and extended the application to a wider range of iodinated carboranes. By the use of Herrmann’s catalyst in toluene at 100 °C this [125I]-iodide labelling could be improved and extended. 2-I-p- 9-I-m-, 9-I-o-, 3-I-o-carborane, 1-phenyl-3-I-o-carborane and 1,2-diphenyl-3-I-o-carborane could be [125I]-iodide labelled in high to excellent yields within 5 minutes.This reported palladium catalyzed radio-iodination of the uncharged closo-carboranes might find use in pharmacokinetic studies of carborane derivatives.
Ciccolini, Cecilia. "Synthesis of Mono and Poly-Heterocycles starting from 1,2-Diaza-1,3-Dienes (or precursors) as Building Blocks." Doctoral thesis, Urbino, 2020. http://hdl.handle.net/11576/2674162.
Повний текст джерелаBELLOSTA, DECHAVANNE VERONIQUE. "Contribution a l'etude de la reactivite de derives glucidiques vis-a-vis d'organometalliques : nouvelles syntheses stereospecifiques de c-glycosides." Paris 6, 1987. http://www.theses.fr/1987PA066256.
Повний текст джерела"Platinum and palladium complexes in arylation and silicone-forming reactions." Tulane University, 2001.
Знайти повний текст джерелаacase@tulane.edu
Nath, Dinesh. "Metalated Nitriles: Ligand Exchange and Copper-Catalyzed Reactions." 2013. http://digital.library.duq.edu/u?/etd,162308.
Повний текст джерелаBayer School of Natural and Environmental Sciences;
Chemistry and Biochemistry
PhD;
Dissertation;
Wheelhouse, Richard T., and D.-F. Shi. "Novel, High-yielding Synthesis of meso-Substituted Porphyrins via the Direct Arylation of Porphine." 2002. http://hdl.handle.net/10454/3620.
Повний текст джерелаA new method for the synthesis of meso-substituted porphyrins is described: reaction of 5,10,15,20-tetrabromoporphine magnesium complex with aryl or heteroaryl boronic acids in the presence of Pd(PPh3)4 gave meso-substituted porphyrins in yields up to 70%.
Rippel, Rafael Alves. "Exploring The benziodoxole Chemistry: New Routes for old Reactions." Master's thesis, 2017. http://hdl.handle.net/10362/25690.
Повний текст джерелаPeng, Yi-Kai, and 彭奕愷. "Facile Synthesis of Benzotrithiophene-Centered HTMs for Perovskite Solar Cells by Pd-Catalyzed C-H Activation/Arylation Reactions." Thesis, 2018. http://ndltd.ncl.edu.tw/handle/5panp9.
Повний текст джерела國立中央大學
化學工程與材料工程學系
106
We develop new benzotrithiophene (BTT)-base hole-transporting materials, synthesized by 3-fold C-H/C-Br cross-couplings. We use benzotrithiophene as middle core and 3,4-ethylenedioxythiophene (EDOT) as π-linker. In the end group, we use triphenylamines as donors. The reaction conditions have been optimized by several entries and all HTMs have good yields. Perovskite solar cells based on the new HTM YKP03, which has EDOT as π-linker, achieve 14 % of power conversion efficiency with dopants and get over 13 % of PCE under dopant-free condition. Another HTM YPK05, which has t-butyl groups as function groups, shows great thermal stability and gets over 15 % of PCE in perovskite solar cells. These results indicate that the new HTMs have potential to be used in perovskite solar cells due to the less synthetic steps and avoiding to use hygroscopic dopants, making the elements become more economical and more stable comparing with the normally used HTM Spiro-OMeTAD.
Friedman, Adam Alexander. "Rhodium and Palladium Catalysed Domino Reactions of Alkenyl Pyridines and Alkenyl Pyrazines." Thesis, 2013. http://hdl.handle.net/1807/42841.
Повний текст джерелаBugarin, Cervantes Alejandro. "Metal-Catalyzed Carbon-Carbon Bond Forming Reactions for the Synthesis of Significant Chiral Building Blocks." Thesis, 2011. http://hdl.handle.net/1969.1/ETD-TAMU-2011-05-9390.
Повний текст джерелаLi, Da. "Transition metal-free desulfinative cross-coupling of 2-pyridyl sulfonates with organolithium reagents : mild access to 2-substituted pyridines." Thesis, 2021. http://hdl.handle.net/1866/25438.
Повний текст джерелаBiaryl compounds containing the pyridine moiety represent a ubiquitous structure in both organic and medicinal chemistry. Therefore, finding new and reliable approaches for their synthesis is still of interest. Traditionally, azine containing biaryls are efficiently synthesized via transition-metal catalyzed cross-coupling reactions. However, due to its π-deficient nature, pyridine cannot be easily functionalized at the C-2 position to serve as nucleophile partner. For examples, in the Suzuki-Miyaura cross-coupling reaction, 2-pyridyl boronates are well known for their instability. 2-Pyridyl organometallics undergo electrophilic aromatic substitution poorly. Thus, the synthesis of 2-substituted pyridines remains a challenging task. The first part of the thesis focuses on the recent methods to address the coupling issues of 2-pyridyl nucleophiles in cross-coupling reactions. Of note, the classical methods including Suzuki-Miyaura cross-coupling reactions, C-H activation of N-activated pyridinium species, and direct coupling reaction of pyridine are presented. Alternative approaches using the pyridine moiety as an electrophilic entity in the coupling with organometallic reagents are also discussed. In the second part of the thesis, a transition metal-free desulfinative cross-coupling reaction of 2-pyridyl sulfonates with organolithium reagents is reported. A variety of 2-substituted pyridines were successfully synthesized in good yields, by treatment of neopentyl 2-pyridyl sulfonates and phenyl 2-pyridyl sulfonate with aryl, alkyl, and heteroaryl-lithium reagents at low temperature. Mechanistic studies showed that the coupling reaction with lithium reagents undergoes an SNAr pathway. However, a ligand coupling process of a σ-sulfurane intermediate may be involved in the reaction with Grignard reagents to form the biaryl.
Lee, Yan-Yi, and 李衍毅. "The Use of Isomeric Normal and Abnormal Palladium NHC Complexes in Direct C5-arylation Reaction." Thesis, 2018. http://ndltd.ncl.edu.tw/handle/3fes4m.
Повний текст джерела國立彰化師範大學
化學系
106
We designed four series of isomeric palladium(II) complexes normal and abnormal N-Heterocyclic Carbenes (NHCs) ligands. These complexes were characterized by 1H and 13C NMR spectroscopy, elemental analysis and X-ray crystallography. Their potential application as catalysts in direct C5-arylation reaction between imidazoles and aryl halides were investigated. Using a mere 0.5 mol % Pd loading, coupled products were obtained with moderate to excellent yields. Normal NHCs complexes have better catalytic activity than their abnormal counterpart. DFT calculations were performed to explain the difference.
Lin, Wu-Shien, and 林武賢. "Palladium Complexes with N-heterocyclic Carbene and Phosphine Ligands: their Catalytic Application in Direct Arylation Reaction." Thesis, 2010. http://ndltd.ncl.edu.tw/handle/80528611956437786449.
Повний текст джерела國立彰化師範大學
化學系
98
The new palladium complexes with NHC and phposphine ligand, PdR2(NHC)(PR'3) were prepared from the reactions between ligand precursors with different steric effect and PdCl2(COD). New derivatives were prepared by the ligand substitution reaction between PPh3 and PCy3, bipyridine, and acetate. All the complexes were successfully characterized by X-ray crystallographic studies and NMR, illustrating the structural difference due to the ligand structures. Interesting intramolecular interactions were found in some of these complexes. To understand the relative stability between the cis and the trans forms, we conducted density functional theory computations. In catalytic investigations, the new complexes were test as precatalysts for Suzuki, Heck coupling reaction, and direct arylation reaction. Unfortunately the yields were not good in Suzuki coupling reaction; the working temperature was too high. But we get outstanding yields in direct arylation reactions. Initially, complexes were screened as precatalysts for the direct arylation reactions between aryl halides and alkynes. Then we utilized wide scope of reactants to test our compounds’ activities. Excellent performance was achieved. We also tested new direct arylation reactions using imidazole derivatives, and proved that the complexes were also quite effective. In short, we find these complexes having remarkable success in direct arylation reactions.
Hou, Wen-Yi, та 侯文易. "Palladium-Catalyzed α Arylation Reaction of Cyclic Vinylogous Esters: Total Syntheses of Aromatic Podocarpane-type Diterpenoids". Thesis, 2017. http://ndltd.ncl.edu.tw/handle/99977t.
Повний текст джерела國立交通大學
應用化學系碩博士班
105
The first part of this thesis describes palladium-catalyzed α-arylation reaction of cyclic vinylogous esters. The commercial 1,3-cyclohexedione (81) was undergo three times alkylation on the different atoms of compound 81 to get the vinylogous esters 86. We examined several reaction parameters and found the optimal condition called for the combination of Pd(dba)2 and tBuP3 and lithium dicyclohexylamide acting as a base. The optimized conditions were utilized to conduct the coupling reaction between a vinylogous ester and bromoarenes. Electron-deficient and Electron-rich bromoarenes were effective coupling partners, the corresponding products are compound 100~106. It is noteworthy that the arylation is compatible with a sterically demanding ortho-substituted substrate, albeit at a slower rate (compound 107). We examined the compatibility of heterocyclic bromides in this transformation and it can be applied with good yield and the corresponding products are compound 108~112. The second part is describle total syntheses of aromatic podocarpane-type diterpenoids. A conjugated dienone 145 was prepared from the arylated product 104 via a Stork−Danheiser transposition that comprises sequential 1,2-addition of vinylmagnesium bromide and acidic hydrolysis. Lewis acid-promoted intramolecular Friedel−Crafts reaction of the dienone 145 led to the formation of a tricyclic compound 146. Reductive alkylation of the tricyclic compound under birch conditions provided the desired trans-decalin system bearing the gem-dimethyl moiety 142. Then, the facile removal of the O-methyl group with boron tribromide delivered racemic 12-hydroxy-13-methylpodocarpa-8,11,13- trien-3-one (133). Following reduction in excellent diastereoselectivity, thus accomplishing the first total synthesis of racemic 3β,12-dihydroxy-13-methyl -podocarpane-8,11,13-triene (134). Finally, we showed that (±)-O-methyl nimbinone (135)could be prepared via benzylic oxidation of compound (±)-142.