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Dissertations / Theses on the topic 'Indoles'
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1
Scott, Karen Ann. "Synthetic studies related to the synthesis of vincristine." Thesis, University of Strathclyde, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.367067.
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Martin, Tracey. "Claisen rearragements in indoles." Thesis, Imperial College London, 1986. http://hdl.handle.net/10044/1/38097.
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Stempel, Erik [Verfasser]. "Construction of cyclohepta[b]indoles in the total synthesis of indole alkaloids / Erik Stempel." Hannover : Technische Informationsbibliothek (TIB), 2017. http://d-nb.info/1137165995/34.
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Keech, Peter George. "Electrochemical oxidation of simple indoles." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2001. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp04/MQ61917.pdf.
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Mascal, Mark James. "Synthesis of 3,4-bridged indoles." Thesis, Imperial College London, 1989. http://hdl.handle.net/10044/1/47561.
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Jennings, Peter. "Photophysical study of electropolymerised indoles." Thesis, University of Edinburgh, 1999. http://hdl.handle.net/1842/12295.
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Harrison, Carrie-Ann. "Synthetic approaches to tremorgenic indoles." Thesis, Loughborough University, 1994. https://dspace.lboro.ac.uk/2134/32532.
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The literature on the synthesis of tremorgenic indoles is reviewed in Chapter 1. These compounds are of great importance to agriculture, especially in New Zealand and the United States of America, as they affect the central nervous system of livestock grazing infected pastures. The research centres on the synthesis of lolitrem B, a ten ring structure containing a central indole moiety. The central indole moiety is common for all of the tremorgenic indoles. To this end, studies on the preparation of a trans-fused hydrindane system and its incorporation into the central indole moiety are discussed in Chapter 2. Chapter 3 details investigations into the preparation of a pyrrole from a model used for the hydrindane system. Once obtained, the pyrrole is modified to give the pyranopyrrole, which, in turn, is reacted with dienophiles in Diels-Alder cycloadditions to give substituted indoles. Utilising the model for the hydrindane, studies on the Fischer indole reaction were undertaken to give substituted indoles. Modification of these led to the synthesis of the left-hand side of paspalitrem B. This work is discussed in Chapter 4. Preparation of the tetrahydrofuran portion of lolitrem B and incorporation onto the central indole moiety is detailed in Chapters 3 and 4.
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El, Marrouki Dalel. "Contribution à l’étude de la réactivité de quelques accepteurs de Michael cycliques et applications." Electronic Thesis or Diss., Université de Lorraine, 2020. http://www.theses.fr/2020LORR0197.
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Ce mémoire de thèse se concentre sur la synthèse d’hétérocycles azotés à partir d’une même famille de précurseurs : les 1,4-dicétones. Ces dernières ont été obtenues à travers deux voies de synthèse dont la première consiste en une réaction de Nef permettant la conversion des composés nitrés en cétones. La deuxième est une réaction de Wittig en utilisant divers ylures de Wittig et la cyclohexanedione. Ces intermédiaires réactionnels ont été utilisés par la suite pour la synthèse de dérivés indoliques via une réaction d’addition-1,2. Nous avons également pu orienter la sélectivité de la réaction vers la synthèse des indolones à partir d’une réaction d’addtion-1,4. En présence d’hydrazine monohydrate, les 1,4-dicétones ont aussi permis l’accès à des cinnolines avec d’excellents rendementsThis thesis focuses on the synthesis of some nitrogenous heterocycles from the same family of precursors: 1,4-diketones. These 1,4-diketones have been obtained either by a Nef reaction through the conversion of nitro compounds into ketones or by a Wittig reaction using various Wittig ylides and cyclohexanedione. These reaction intermediates were subsequently used for the synthesis of indole derivatives via a 1,2-addition reaction. We were also able to turn the selectivity of the reaction towards the synthesis of indolones from a 1,4-addition reaction. With hydrazine monohydrate, 1,4-diketones have also provided access to cinnolines in excellent yields
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Hammoud, Sokaina. "Accès à de nouvelles structures tricycliques di-iodes à base indolique et isoindolique par iodocyclisation." Thesis, Tours, 2015. http://www.theses.fr/2015TOUR4034.
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Une nouvelle voie d’accès à des structures tri-cycliques originaux les « oxazino-indole di-iodés» a été mise au point à partir des acides 1H-indole-2-carboxyliques commerciaux ou des acides 1H-indole-2-carboxyliques fonctionnalisés obtenus par la réaction d’Hemetsberger-Knittel. La dernière étape de cette séquence est une réaction d’iodocyclisation qui s’est avérée totalement régio- et stéréosélective selon un processus de type 6-exo-dig. Cette méthodologie a ensuite été étendue en série isoindolique permettant un accès à des motifs « oxazino-isoindolique di-iodés » originaux. Afin d'étendre davantage cette méthodologie, de nouveaux « oxazepino-indole di-iodés » ont été préparés en utilisant la même approche synthétique à partir de l'acide 1H-indole-7-carboxylique. La réactivité des structures tri-cycliques di-iodés a été étudiée via des réactions de Cross-Coupling (Stille, Sonogashira, Suzuki) par l’utilisation de sels de palladium permettant une fonctionnalisation régiosélective de l’iode exocycliqueA new access pathway to the original tricyclic structures "di-iodinated oxazino-indole" was developed from the commercial 1H-indole-2-carboxylic acids or functionalized 1H-indole-2-carboxylic acid obtained by Hemetsberger-Knittel reaction. The last step in this sequence is an iodocyclisation reaction that is proved to be completely regio- and stereoselective via 6-exo-dig process. This methodology was then extended to isoindolic series allowing access to original "di-iodinated oxazino-isoindole" motifs. To further extend this methodology, new"di-iodinated oxazepino-indoles" were prepared using the same synthetic approach from the 1H-indole-7-carboxylic acid. The reactivity of the di-iodinated tri-cyclic structures has been studied via Cross-Coupling reactions (Stille, Sonogashira and Suzuki) by the use of palladium salts allowing a regioselective functionalization of the exocyclic iodine
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Westermaier, Martin. "Electrophilic Substitutions of Indoles and Pyrroles:." Diss., lmu, 2007. http://nbn-resolving.de/urn:nbn:de:bvb:19-77431.
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Beck, Anthony Leonard. "Synthetic routes to (cd)-fused indoles." Thesis, Imperial College London, 1990. http://hdl.handle.net/10044/1/47769.
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Joãoa, Heidi. "Synthesis of pyrrolobenzothiadiazepines, pyrrolizidines and indoles." Thesis, University of Huddersfield, 2014. http://eprints.hud.ac.uk/id/eprint/23691/.
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In this thesis, novel syntheses of analogues of pyrrolobenzodiazepines (PBDs) are described. These compounds are of great interest as synthetic targets due to their potential medical properties. The first process involved is the intramolecular 1,3‐dipolar cycloaddition between the azide and imine present to form the PBD core, a process that occurs via cycloaddition and extrusion of nitrogen. An azide to nitrile cycloaddition was also explored. As an extension to azide work, a series of 2‐azidobenzenesulfonamides with homoallylic substituents were investigated as precursors in aza‐Prins reactions. Although this was unsuccessful, it led to the observation of an interesting transamination type process. The attempted synthesis of the sulfur analogues of Fuligocandins A and B are also discussed. Fuligocandin B is known to sensitise leukaemia cells to apoptosis and thus analogues are worthy targets. Synthetic ease drove us to apply the Eschenmoser episulfide contraction to the synthesis of analogues. The thesis includes the synthesis of other pyrrolo‐fused systems with a focus on the indolizidines and pyrrolizidines. These were prepared from the reaction of a cyclic imine with diphenylcyclopropenone (DPP) as illustrated in the Scheme. The imines were reacted with DPP to study the effect of a large substituent at position 3 to investigate its effect on the stereochemical outcome of the reaction. While accessing these indolizidines we serendipitously synthesised several examples of indoles and quinoline systems.
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Hubbard, Jeremiah W. "Novel synthesis of 3,4-fused indoles." Morgantown, W. Va. : [West Virginia University Libraries], 2001. http://etd.wvu.edu/templates/showETD.cfm?recnum=2209.
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Thesis (M.S.)--West Virginia University, 2001.Title from document title page. Document formatted into pages; contains xi, 70, 76 p. : ill. Includes abstract. Includes bibliographical references (p. 67-70).
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BRAMBILLA, ELISA. "METAL-CATALYZED SYNTHESIS OF POLYCYCLIC INDOLES." Doctoral thesis, Università degli Studi di Milano, 2021. http://hdl.handle.net/2434/819484.
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The indole core is ubiquitous in bioactive natural products and pharmaceutical compounds and the chemistry of the indole nucleus is the subject of intense investigations both for the synthesis of the indole core and the functionalization at both pyrrole and benzene moieties. One of the most employed building blocks is 2-vinylindole that pertains to the class of heterocyclic internal-external ring dienes, a useful class of molecules able to take part in cycloadditions with various dienophiles providing an easy access to poly(hetero)cycles. Another interesting compound, is 4H-furo[3,2-b]indoles presenting the peculiar structure of 4π-system embedded in the furan ring, leading to an increase of reactivity in comparison to 2-vinylindole congeners. Thus, potentially, 4H-furo[3,2-b]indoles could take part in different cycloaddition reactions as dienes when employed in [4+2] or (4+3) cyclizations or as dienophilic partners in [2+2] reactions with the C1-C2 double bond of the furan moiety. Furthermore, the C2 carbon of furan shows nucleophilic properties and can participate in simple functionalization reactions with different electrophiles. Moreover, as reported for simple furan derivatives, the addition of an electrophile at C2 can be followed by rearrangement processes that include a ring opening step. Thus the thesis is focused on the synthesis of different functionalized 4H-furo[3,2-b]indoles and on the study of their reactivity in the presence of different electrophilic partners. In detail, the obtained results belong to three main research topics: the first part was focused on the gold activation of different π systems for the synthesis of indole derivatives from 4H-furo[3,2-b]indoles. In particular, it reports the cationic gold(I) catalyzed cascade reactions of 4H-furo[3,2-b]indoles with allenamides for the synthesis of spiropseudo-indoxyls. Successively, the activation of propargyl esters by gold(I) catalysts led to the synthesis of 2-alkenylidene-3-oxoindoles in a process that included a furan ring rearrangement. The second part reports the behavior of 4H-furo[3,2-b]indoles in the presence of a different electrophile, a copper(I) carbene, obtained from the in situ decomposition of a diazo compound under copper catalysis. The reaction allowed for the formation of a homologous series of the previously cited 2-alkenylidene-3-oxoindoles presenting a less extended conjugate system. The last part is focused on the in situ generation of an oxyallyl cation in order to study the performance of 4H-furo[3,2-b]indoles in (4+3) cycloaddition reactions. In this case, the electrophile was obtained from a α-haloketone under basic condition and then reacted with both 2-vinylindoles and 4H-furo[3,2-b]. In addition, some preliminary results on the study of the reactivity of benzo[c]isoxazoles (anthranils) under basic condition for the synthesis of 2-hydrazineylisophthalaldehydes were conducted.
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Jonsson, Ann-Louise. "Synthetic studies of marine indole alkaloids and related systems /." Stockholm, 2005. http://diss.kib.ki.se/2005/91-7140-587-9/.
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Rodriguez, Dominguez Juan Carlos. "Nouvelles synthèses de dérivés hetérocycliques pour applications biologiques : (Céphalosporines, Coumarines et Indoles) = New synthesis of heterocyclic derivatives for biological applications (Cephalosporins, Coumarins and Indoles)." Metz, 2006. http://docnum.univ-lorraine.fr/public/UPV-M/Theses/2006/Rodriguez_Dominguez_Juan_Carlos_SMZ0618.pdf.
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Les céphalosporines de synthèse, les dérivés de coumarines et indoles sont des composés très intéressant dans le domaine de la biochimie. Les premières sont utilisées habituellement dans le système de santé mondiale contre les infections bactériennes ; les secondes et les dernières, sont présentes dans les sciences de la nature et de la vie avec des larges gammes d'activités et des usages biologiques. Due à leurs importantes applications, il apparait nécessaire d'avoir des méthodes efficaces pour synthétiser ces produits. Des temps de réactions plus courts, de bons rendements, un travail fait dans des conditions respectueuses de l'environnement, sont les aspects principaux pour diminuer les coûts des produits finaux. Dans ce travail nous développons des procédures synthétiques améliorées afin d'obtenir des antibiotiques céphalosporiniques de troisième génération, des coumarines et des acétates de 1-acétyle-indole-3-yl. La plupart de ces procédures réduisant les étapes de synthèse, le temps de réaction avec une augmentation sensible des rendements; les autres, introduisant quelques catalyseurs hétérogènes amenant les produit: finaux avec de bons rendements, similaires à ceux-là de la littérature sans avoir à traiter de résidus toxiquesSemisynthetic cephalosporins, coumarins and indoles derivatives are very valuable compounds in the biochemical branch. The firsts commonly used in the world health system against bacterial infections; the second and last ones, presents in nature and life sciences with wide spectra of biological activities and uses. Due their important applications it is necessary to count with appropiated methods of synthesis in order to obtain them. Shorter reactions time with good yields and as always as possible, in a friendly environment work up, are the main aspects to shoot down the costs of the final products. In this work we develop some improved synthetic procedures in order to obtain some cephalosporani-antibiotics of third generation, coumarins and (1-acetyl-indol-3-yl) acetates, the most part of them reducin! steps and time with a sensitive increase in yields; others, introducing some heterogeneus catalysts bringin ! the final products up with similar yields to those from literature with not toxic waste to treat
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Wu, Ju. "Electrochemical and Non-electrochemical Oxidative Dearomatization Reactions of Indoles." Thesis, Université Paris-Saclay (ComUE), 2019. http://www.theses.fr/2019SACLS368.
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L'électrochimie est apparue comme un puissant outil de synthèse durable en chimie organique, qui évite l'utilisation d'un oxydant stoechiométrique externe et permet le développement de méthodes de difonctionnalisation très efficaces et sélectives des indoles dans des conditions douces. L'utilisation de médiateurs redox pour réaliser l'électrolyse indirecte a gagné en importance ces dernières année, ce qui offre de nombreux avantages par rapport à l'électrolyse directe. Les réactions de désaromatisation des hétéroarènes achiraux, et en particulier des indoles, donnent des structures tridimensionnelles d’un grand intérêt pour la synthèse totale ou la découverte de médicaments, via la génération de deux centres stéréogéniques contigus. Ainsi des efforts de synthèse intensifs ont été consacrés à la difonctionnalisation désaromatisante d’indoles. Dans ce contexte, le développement de réactions de désaromatisation des indoles a été étudié au cours de cette thèse. Dans la première partie de la thèse, une diallylation désaromatisante de N-acylindoles médiée par FeCl₃ a été développée pour obtenir des indolines tridimensionnelles sélectives possédant deux centres stéréogéniques contigus. Dans ce procédé, deux groupes allyle ont été introduits sur des N-acylindoles avec de l'allyltriméthylsilane en présence de FeCl₃, conduisant à la formation de deux liaisons carbone-carbone et de deux centres stéréogéniques contigus. La stéréosélectivité de cette transformation est contrôlée par la substitution du noyau indole. Des applications synthétiques ont permis d'obtenir des squelettes trans-tétrahydrocarbazoles et aza[4.4.3]propellanes par RCM. L'hydratation sélective de l'un des groupes allyliques a également été réalisée. Dans la deuxième partie de la thèse, une désomatisation oxydante directe des indoles a été réalisée par électrochimie, conduisant à des 2,3-dialcoxy ou des 2,3-diazido indolines avec une cellule non divisée à courant constant. Cette difonctionnalisation électrochimique des indoles évite l'utilisation d'un oxydant externe et présente une excellente compatibilité de groupes fonctionnels, ce qui devrait inspirer le développement d'autres réactions de désaromatisation afin d'accéder à des architectures à haute valeur ajoutée à partir de matériaux de départ facilement disponibles. Sur la base de l'étude mécanistique, nous pensons que la formation des deux liaisons C-O ou C-N résulte de l'oxydation des indoles en un intermédiaire radical cation. Dans la troisième partie de la thèse, une désaromatisation oxydante par électrolyse indirecte des indoles a été conçue en utilisant MgBr₂ comme médiateur redox pour éviter l'oxydation directe du noyau indole à l'anode. L’oxydation de l’indole en un ion bromonium induite par la génération d’un réactif électrophile bromé à partir de MgBr₂, conduit à des réactions de dihydroxylation, d’hydroxycyclisation et de bromocyclisation d’indoles. Aucun sous-produit organique n'est généré avec ce protocole qui ne nécessite aucun électrolyte supplémentaire. L’intérêt de cette transformation est démontré par les applications synthétiquesElectrochemistry emerged as a powerful sustainable synthetic tool in organic chemistry, which avoids the use of an external stoichiometric oxidant and enables the development of methods for the highly efficient and selective difunctionalization of indoles in mild conditions. The use of redox mediators to achieve indirect electrolysis is attaining increased significance, which offers many advantages compared to direct electrolysis. Dearomatization reactions of achiral heteroarenes and in particular of indoles, afford three-dimensional structures of high interest for total synthesis or drug discovery, through the generation of two contiguous stereogenic centers. Intensive synthetic efforts have been devoted to dearomative difunctionalization of indoles. In this context, the development of dearomatization reactions of indoles has been studied in this thesis. In the first part of the thesis, a dearomative diallylation of N-acylindoles mediated by FeCl₃ was developed to obtain selectively three-dimensional indolines possessing two contiguous-stereogenic centers. In this process, two allyl groups were introduced to N-acylindoles with allyltrimethylsilane in the presence of FeCl₃, leading to the formation of two carbon-carbon bonds and two contiguous-stereogenic centers. The stereoselectivity of this transformation is controlled by the substitution of the indole nucleus. Synthetic application allowed to obtain trans-tetrahydrocarbazoles and aza[4.4.3]propellane scaffolds by RCM. Selective hydration of one of the allyl group was achieved. In the second part of the thesis, a direct oxidative dearomatization of indoles was performed with electrochemistry, leading to 2,3-dialkoxy or 2,3-diazido indolines under undivided cell conditions at a constant current. This general difunctionalization of indoles avoids the use of an external oxidant and displays excellent functional group compatibility, which should inspire the development of other dearomatization reactions to access high added-value architectures from readily available starting materials. Based on the mechanistic study, the formation of the two C-O or C-N bonds is believed to arise from the oxidation of the indoles into radical cation intermediates. In the third part of the thesis, an indirect oxidative dearomatization of indoles was devised by using MgBr₂ as the redox mediator to avoid the direct oxidation of the indole nucleus at the anode. The oxidation of the indole into a bromonium ion induced by the generation of an electrophilic bromine reagent from MgBr₂, and lead to dihydroxylation, hydroxycyclization and bromocyclization reactions of indoles. No organic byproducts are generated with this protocol which requires no additional electrolyte. The potential of this transformation is demonstrated by synthetic applications
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Jones, Graham Barry. "Cyclopropamitosenes and related pyrrolo[1,2-a]indoles." Thesis, Imperial College London, 1989. http://hdl.handle.net/10044/1/47491.
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Cowell, Joseph. "Diels-Alder/ene reactions of 3-vinyl-1H-indoles : rapid synthesis of unsaturated carbazoles and pyradazino[3,4-b]indoles." Thesis, University of Newcastle upon Tyne, 2014. http://hdl.handle.net/10443/2719.
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Unsaturated carbazole frameworks are found in several important naturally occurring and synthetic biologically active compounds. We envisaged synthesising compounds of this type using an intermolecular Diels-Alder reaction between 3-vinyl-1H-indole and a dienophile, followed by an intermolecular ene reaction between the resultant Diels-Alder adduct (6) and an enophile. This route was tested using tosyl protected 3-vinyl-1H-indole (4) and N-methylmaleimide (5) in a Diels- Alder reaction, followed by ene reactions with a range of enophiles to give unsaturated carbazoles (7) in yields of 50-60% over the two steps. Through utilisation of Soos’s organo-catalyst3, we have been able to control the Diels-Alder reaction between 3-vinyl-1H-indole (8) and N-methylmaleimide (5), to form the Diels-Alder adduct (9) with high enantiomeric excess. The subsequent stereospecific ene reaction then gives unsaturated carbazoles (10) in >96% ee. We then developed a sequential “one-pot” Diels-Alder / ene methodology with an Nprotected 3-vinyl-1H-indole (11), a dienophile and an enophile to make unsaturated carbazoles and pyridazino[3,4-b]indoles (13). This methodological approach gave increased overall yields and reduced purification steps. When Cbz N-protected 3-vinyl-1H-indoles were used the Diels-Alder / ene products (14) could then be deprotected through a PtO2 catalysed hydrogenation reaction to give molecules (15). Several of the synthesised compounds (15) showed moderate biological activity against Escherichia coli, Staphylococcus aureus and Schizosaccharomyces pombe. Compounds (15) are also moderate (μM) inhibitors of several important kinases, including Chk2, Aurora B, Src and JAK2, which are potential targets for cancer treatment.
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Rehn, Stanley. "Synthesis of indole and oxindole derivates incorporating pyrrolidino, pyrrolo or imidazolo moieties /." Stockholm, 2004. http://diss.kib.ki.se/2004/91-7140-169-5/.
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Wahlström, Niklas. "Synthesis of indoles, bisindoles and indolocarbazoles : high affinity aryl hydrocarbon receptor ligands /." Stockholm, 2004. http://diss.kib.ki.se/2004/91-7140-016-8/.
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Mondière, Aurélie. "Réactions multicomposants et applications : synthèse de cyclopent[b]indoles et pyrrolo[1,2-a]indoles : synthèse diastéréosélective de lignanes tétrahydrofuraniques trisubstitués." Phd thesis, Université Claude Bernard - Lyon I, 2010. http://tel.archives-ouvertes.fr/tel-00837814.
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Ce mémoire de thèse est composé de deux parties distinctes ayant comme thématique commune, les réactions multicomposants (MCR). Nous nous sommes intéressés dans un premier temps au développement d'une nouvelle MCR conduisant à des dérivés de l'indole, hétérocycle rencontré dans de nombreuses substances naturelles et composés biologiquement actifs. Nous avons ainsi mis au point un nouvelle méthodologie MCR séquentielle, rapide et efficace permettant d'accéder sélectivement, à partir des trois mêmes substrats (un précurseur indolique, un alcyne vrai et un accepteur de Michael) à deux familles de composés : les cyclopent[b]indoles ou les pyrrolo[1,2-a]indoles par une simple inversion de l'ordre des réactions. Puis dans un deuxième temps, nous avons élaboré une nouvelle synthèse totale diastéréosélective de lignanes tétrahydrofuraniques trisubstitués, connus pour leur abondance dans la nature et leurs propriétés biologiques très variées. Cette synthèse courte est composée de trois étapes clés : une réaction de cyclofonctionnalisation multicomposants palladocatalysée, une déméthoxycarboxylation -élimination utilisant des conditions de Krapcho modifiées et une réaction de type Hayashi-Miyaura permettant d'introduire le deuxième groupement aryle. Cette dernière réaction d'addition conjuguée a représenté le défi de cette synthèse et a donc fait l'objet d'une étude particulière sur un substrat modèle.
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Somphol, Kittiya Chemistry Faculty of Science UNSW. "Synthesis of new heterocyclic structures based on indoles." Awarded by:University of New South Wales. Chemistry, 2007. http://handle.unsw.edu.au/1959.4/40829.
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Novel indolo-macrocycles have been generated from the attempts to synthesise bis-indolo-cyclotriveratrylenes by the condensation of I, I'-diindolyl-3,3'-dimethanols catalysed by p-toluenesulfonic acid. The addition of substituents on indoles led to enhanced solubilities of the macrocycles. Nine- and six-membered ring compounds have been synthesized from the acid-catalysed reaction of I,I'-diindolyl compounds and aryl aldehydes. Some reactions of these compounds and the attempted synthesis of 2,2' diindolylmethanes from the cyclic compounds have also been described. The electrophilic substitution reactions of 3-substituted 4,6-dimethoxyindole 2,6-dimethanols and 3-substituted 4,6-dimethoxyindole-7 and 2-carbaldehydes and I-substituted indoles afforded triindolyl dialdehydes. The wriation of substituents at C-7 of indole-7-aldehydes and at C-2 of indole-2-aldehydes has also been discussed. Reaction of the hydroxymethylindole and 1,2-di(indol-I-ylmethyl)benzene gave a new macrocycle. Substitution reactions of 2,2???-diindolylmethane-7,7'-dimethanol and indole-7- and 2-aldehydes gave tetraindolyl dialdehydes. Sodium borohydride reduction of tri- and tetra-indolyl dialdehydes gave tri- and tetra-indolyl dimethanols respectively. Acid-catalysed reactions of tri- and tetra-indolyl dimethanols afforded only calix[3] and [4]indoles respectively when all substituents at C-3 of indoles were aryl groups. New conditions for indole based imine synthesis have been established Macrocyclic imine formation from mono-, di-, tri and tetra-indolyl dialdehydes has been investigated. Reactions of indole-3, 7-dialdehydes and short chain diamines (1,2-diaminoethane, 1,2-diaminobenzene and 1,6-diaminohexane) gave mixtures while the reactions with long chain diamines (1,10 diaminodecane and 1,12-diaminododecane) gave monoindolyl macrocyclic imines. Reaction of indole-2, 7-dialdehydes and short chain diamines afforded diindolyl macrocyclic imines with head-tail structures, and the 2,7';2',2";7",2'''-Tetraindole-7 ,7"'-dialdehyde underwent cyclisation with triindolyl dialdehydes and 1,6-diaminohexane afforded triindolyl macrocyclic imines. 1,2 diaminoethane while the 2,3 ';1',1 ";3 ",2"'-tetraindole-7,7"'-dialdehydes underwent imine, with its precise structure established by X-ray crystallography. Reaction of of 1,3-di(indol-l-ylmethyl)benzene and 1,2 diaminoethane yielded a new macrocyclic reactions with long chain diamines yielded monoindolyl macrocyclic imines. Reaction ring closure with 1,2 diaminoethane and 1,6-diaminohexane.
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Voro, Tevita N. "Synthesis of potentially biologically active indoles and pyrroles." Thesis, University of East Anglia, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.254485.
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Tidwell, Jeffrey H. "Synthesis of indoles via zirconocene-stabilized benzyne complexes." Thesis, Massachusetts Institute of Technology, 1994. http://hdl.handle.net/1721.1/17369.
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Kettle, Lorna J. "A computational and electrochemical study of electropolymerised indoles." Thesis, University of Edinburgh, 2000. http://hdl.handle.net/1842/15164.
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The electropolymerisation of a range of 5-substituted indoles results in the formation of redox active films. The redox species present in the film have been characterised as the asymmetric trimer. These films are observed to be extremely photoluminescent and the chief fluorophore has been identified as the trimer. Initial studies have involved electrochemical and photophysical investigation with a view to potential application as fast response potentiometric sensors or as materials for light emitting devices. This thesis extends this work by presenting a computational and electrochemical study of a range of electropolymerised 4-, 5-, 6-, and 7-substituted indoles. This research has employed the powerful combination of computational quantum chemical methods with electrochemical techniques to explore the electronic structure of the 5-substituted indoles. Density Functional Theory and semi-empirical calculations have shown that it is possible to predict oxidation potentials to within ±0.1eV of the experimental values. Calculations of the electronic structure of the monomer radical cation, the species involved in trimer formation, has shown a difference in the calculated p-spin density distribution between indoles with electron withdrawing substituents and indoles with electron donating substituents. For those withdrawing groups the unpaired electron is located at the 3-position which is consistent with the formation of a dimer via 3,3-'linkage in the initial stages of polymerisation. For indoles with electron withdrawing substituents the chief location of the unpaired electron in the radical cation is near the substituent consistent with previous experimental observation that trimerisation of these indoles will only occur on the surface of a preformed trimer film. The electronic structure of the indole radical cation has been probed by studying the effect of the substituent nature and position. The electrooxidation of a various 4-, 6- and 7-substituted indoles result in redox films consisting of novel indole trimers. The monomers and electropolymerised films are photoluminescent and the common fluorophore observed infers that the chief fluorophore in the films are indole trimers. Quantum chemical methods predict oxidation potentials of these indoles in good agreement to experimental values. The transmission of substituent electronic effects through the aromatic system of the indole radical cations is again different for electron withdrawing and electron donating substituents.
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Aboutayab, Karim. "Novel methods for the synthesis of functionalised indoles." Thesis, University of Sussex, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.262319.
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The work in this thesis describes investigations into the development of a tandem radicallDiels-Alder reaction strategy for the construction of indole alkaloids. The synthesis of a key precursor, 2-[(4-methylphenyl)sulfonyl]indole, was investigated and involved two main· strategies: functionalisation of the indole ring using lithiation procedures and assembling the indole as a key step (chapter 2). A method based on the former strategy was deemed to be the most practical and delivered the desired product in moderate yields (35 - 45%). The viability of the first step of the proposed tandem radicallDiels-Alder strategy was investigated by examining the intramolecular addition of vinyl and aryl radicals to a sulfone substituted indole (chapter 3). These studies showed that the addition of sp2 centred radicals to substituted indoles was feasible (20 - 40%). A study using an acetylenic precursor also provided useful information about the relative rates of desulfonylation and radical addition to acetyleneS; de-sulfonylation is a competing process. An alternative tandem palladiumlDiels-Alder reaction was briefly examined, but was thwarted by capricious palladium catalysed cross coupling reactions. Further studies were carried out to extend the scope of the novel ipso substitution reaction (chapter 4). It was found that alkyl radical cyclisations proceed efficiently to give a new ~ethod for the synthesis of fused[1,2-a]indoles (30 - 84%). The feasibility of a related ipso substitution using phenylthio and phenylsulfinyl substituted indoles was also examined. It was found that these reactions are also successful, but proceed in reduced yields compared with the sulfones (24 - 51 %). These results could be attributed to the more favoured reaction of the electron rich carbon centred radical with the more electrophilic 1t bond. The thesis is concluded by a brief discussion of the mechanism of these cyclisations with the available experimental evidence supporting an addition! elimination pathway.
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Kennedy, Abigail Rose. "The synthesis of highly substituted indoles via isonitriles." Diss., The University of Arizona, 2001. http://hdl.handle.net/10150/290368.
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A highly efficient approach to 2,3-disubstituted indoles has been presented. The indole precursors, isonitriles, were used as powerful geminal radical donors/acceptors. The novel isonitrile-alkyne free radical cascade has been efficiently mediated by tin and sulfur. In the case of sulfur, interesting 2,3-dithioindoles were formed. This new class of compounds has exhibited great promise as versatile indole intermediates. In particular, nucleophilic additions at C-10 of the 2,10-dithioindoles were achieved using carbon, sulfur and amine nucleophiles. The versatility of 2,10-dithioindoles was further demonstrated using rhodium-mediated sulfur ylide chemistry. We achieved an intramolecular sulfur ylide reaction which led to a gramine-type addition product 270. Furthermore, sulfur ylides were formed intermolecularly and rearranged to give highly substituted indoles. In studies aimed at the synthesis of the spirotryprostatins, our 2,10-dithioindoles were used in the synthesis of both a simple C-3 spiro-oxindole compound 249 and a diketopiperazine-containing indole derivative 256. This demonstrated the exciting potential of our indole-forming reaction and elaboration methodologies in natural product synthesis.
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Smith, Valerie J. "Synthesis and pharmacology of N-alkyl-3-(Halonaphthoyl)indoles." Connect to this title online, 2008. http://etd.lib.clemson.edu/documents/1219855380/.
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單慧媚 and Wai-mei Della Sin. "Addition reactions of 3H-indoles and their N-oxides." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1992. http://hub.hku.hk/bib/B31233193.
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Hawe, Samuel Mark. "The production and metabolism of indoles in growing pigs." Thesis, Queen's University Belfast, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.335492.
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Clarke, Aimee. "Dearomatisation reactions and a novel route to substituted indoles." Thesis, University of York, 2018. http://etheses.whiterose.ac.uk/20434/.
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This Thesis describes the development of silver-catalysed dearomatising spirocyclisation reactions of alkyne-tethered aromatic and heteroaromatic systems. An overview of dearomatisation methodologies and spirocyclisation strategies involving alkyne activation are discussed in Chapter 1. Chapter 2 describes a novel silica-supported silver-catalysed spirocyclisation method. This strategy was applied to a range of aromatic ynone systems and mechanistic information suggesting the involvement of silver nanoparticles in the spirocyclisation process is also reported. This silica-supported spirocyclisation reaction was then applied to a range of phenol-tethered ynones furnishing spirocyclic dienone products which is the focus of Chapter 3. Some preliminary asymmetric spirocyclisation studies using silver salts of chiral phosphoric acids (CPAs) are also described as well as a formal synthesis of the natural product spirobacillene A. A novel Ag(I)-catalysed synthesis of substituted indoles using pyrrole-tethered alkynes is detailed in Chapter 4. Density functional theory (DFT) calculations are described which suggest that benzannulation proceeds initially via spirocyclisation at the pyrrole C-3 position before undergoing subsequent rearrangement to deliver the indole products. Chapter 5 describes the divergent reactivity of phenol-/anisole-tethered α-diazocarbonyls. Four products (cyclopropanes, tetralones, 1,2-dicarbonyls and spirocycle) were accessed through distinct reaction pathways in which the outcome was dependent on the catalyst used and the nature of the aromatic oxygen substituent.
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Peat, Andrew J. E. 1970. "Novel approaches to functionalized indoles and polysubstituted aromatic compounds." Thesis, Massachusetts Institute of Technology, 1997. http://hdl.handle.net/1721.1/10221.
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Lam, Tin Yiu. "Synthesis of indoles via a tandem benzannulation-cyclization strategy." Thesis, Massachusetts Institute of Technology, 2008. http://hdl.handle.net/1721.1/46045.
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Vita.Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2008.
Includes bibliographical references.
Vinylketenes (generated in situ from cyclobutenones or a-diazo ketones) react with ynamides via a pericyclic cascade process to produce highly-substituted aniline derivatives. Cyclization of the benzannulation products can then be achieved via several alternate procedures leading to indoles that are highly substituted on the six-membered ring. The cyclization approaches investigated as the second step in this tandem strategy included aromatic substitution, palladium-catalyzed oxidative amination, and nucleophilic cyclization. This thesis discusses the scope and limitations of this tandem strategy.
by Tin Yiu Lam.
Ph.D.
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Rodriguez, Dominguez Juan Carlos Kirsch Gilbert Prieto Sylvia. "Nouvelles synthèses de dérivés hetérocycliques pour applications biologiques (Céphalosporines, Coumarines et Indoles) = New synthesis of heterocyclic derivatives for biological applications (Cephalosporins, Coumarins and Indoles) /." [S.l.] : [s.n.], 2006. ftp://ftp.scd.univ-metz.fr/pub/Theses/2006/Rodriguez%20Dominguez.Juan%20Carlos.SMZ0618.pdf.
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Benzies, David W. M. "Some aspects of the synthesis and reactions of substituted indoles." Thesis, University of East Anglia, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.232923.
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Brookes, Alastair Forbes. "Development of novel therapies for colorectal carcinoma using dietary indoles." Thesis, University of Leicester, 2014. http://hdl.handle.net/2381/29325.
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Colorectal carcinoma is the third commonest cancer in the UK and is the second commonest cause of cancer related death. There is a need for efficacious chemotherapeutic and chemopreventative agents against colorectal carcinogenesis. Indole-3-carbinol and its acid condensation product, 3,3 diindolylmethane (DIM), exhibit anti-tumourigenic activity in preclinical models. This study investigated their therapeutic potential in colorectal carcinoma. A panel of four colorectal carcinoma cell lines (HT29, HCT116, SW480 and SW620) was used to compare effects of DIM and I3C on cell viability, induction of apoptosis and cell cycle arrest. Treatment with DIM or I3C resulted in dose-dependent reductions in cell viability. Cell lines were sensitive to 25–75 μM DIM (GI[subscript 50] = 45 μM), but not to 200 μM I3C. DIM (40 μM) induced apoptosis in all cell lines. This was associated with downregulation of survivin and appeared to be independent of p53. Furthermore it induced G[subscript 1] arrest in HCT116, SW480 and SW620 and G[subscript 2]/M arrest in HT29. DIM induced activatory phosphorylation of Chk2 in HT29 but not in HCT116. DIM downregulated cell cycle proteins: PLK1, cdc25C, cdc2 and cyclins B1, D1 and E. Since all colon cancer cell lines expressed significant levels of Src, their response to Src inhibition was investigated. Colon cancer cells were modestly sensitive to AZD0530 (AstraZeneca), but combination with indoles reduced viability to a greater extent than single agent treatment. Combining 40 μM DIM with 1 μM AZD0530 was particularly effective, reducing viability by half after 48 hours on average. Decreases were sustained and progressive over extended timepoints. Attempts were made to establish primary cultures from resected hepatic metastases however issues were identified with cell death, fibroblast overgrowth and slow cell turnover. Potential changes to address these were identified. These data suggest chemotherapeutic potential of DIM in colon cancer, particularly in combination with Src inhibition.
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Engqvist, Robert. "Syntheses of some tri- and tetracyclic heterocycles containing an indole moiety /." Stockholm, 2004. http://diss.kib.ki.se/2004/91-7140-161-X/.
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Pchalek, Karin Chemistry Faculty of Science UNSW. "Design and synthesis of new ligands and heterocycles from activated indoles." Awarded by:University of New South Wales. School of Chemistry, 2004. http://handle.unsw.edu.au/1959.4/20584.
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For the purpose of incorporating indoles into organometallic complexes for catalysis, as well as in the generation of new heterocyclic systems, various reactions have been carried out at C2, C6 and C7 of the indole system. In order to achieve this, 3-substituted 4,6-dimethoxyindoles and 6-hydroxy- 4-methoxyindoles were necessary as starting materials. Consequently, a lithium-bromide-templated one-pot procedure for the synthesis of some 3-substituted 4,6-dimethoxyindoles and a selective demethylation procedure for 3-substituted 6-hydroxy-4-methoxyindoles were developed. Various kinds of novel methylene-bridged bi-, tri-, and tetradentate pyridyl-indole ligands were synthesised via Vilsmeier-Haack, Friedel-Crafts or electrophilic addition reactions on the indole heterocycle. However, their metal complexing properties were generally weak and variable. Nevertheless, some of the tridentate pyridylindole ligands showed strong anion binding to halides, whereas a remarkable ligand transformation occurred with a bidentate 2-pyridylindole ligand and zinc(II), giving a substituted indolo[2,3-c]pyrrolo-[3,2,1-ij]quinoline system. Two new types of tetradentate Schiff base ligands were prepared from 2-formyl-indoles and 7-formyl-6-hydroxyindoles, and diamines. These preformed ligands were reacted with first- and second-row transition metals to give neutral metal complexes. Novel heterocyclic systems such as 4H-pyrrolo[3,2,1-ij]quinolines, 3H-pyrrolo-[1,2-a]indoles, and 1H-furo[2,3-g]indoles were synthesised from 2-formyl-, 7-formyl-, and 6-hydroxyindoles, utilising mainly intra-molecular Wittig reactions, Claisen-Schmidt condensations or acid- and base-catalysed cyclisations. A common feature of the prepared 4H-pyrrolo[3,2,1-ij]quinolines and 3H-pyrrolo-[1,2-a]indoles was their intense fluorescent character, which was examined as well.
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Main, Calver A. "Novel titanium carbenoid reagents : diversity orientated synthesis of indoles and spirocycles." Thesis, University of Glasgow, 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.502007.
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A new synthetic strategy for the preparation of a 96-member library of 2,5-disubstituted indoles involving traceless cleavage from resin is presented. A boronate-bearing titanium alkylidene was prepared and used to convert 8 resin-bound esters into immobilised enol ethers. Cleavage from resin in mild acid with concomitant cyclisation yielded boronate-bearing indoles. Capitalising on the immobilised boronate functionality in enol ethers, Suzuki cross-coupling reactions were performed with 12 aryl iodides to give a 96-member library after cleavage from resin with mild acid, 79 members of the library were confirmed to be 2,5-disubstituted indoles. Also reported is the use of tertiary butyllithium and 2-isopropoxy-4,4,i,5-tetramethyl-l,3,2-dioxaborolane to convert an aiyl bromide into an arylboronate in the presence of a dithiane, with simultaneous reduction of an aryl azide to an amine. In a similar route, we synthesised dithiane for the attempted conversion of resin-bound esters into functionalised 7-azaindoles after cleavage from resin. Further investigation with a different ortho-nitrogen protecting group may yet prove successful.
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O'Sullivan, Noeleen. "Synthesis and reactions of cyclopropamitosenes and related pyrrolo[1,2-a]indoles." Thesis, Loughborough University, 1992. https://dspace.lboro.ac.uk/2134/14132.
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The use of Mitomycin C in the treatment of a wide range of neoplastic conditions is discussed. The mechanism of action of mitomycin anticancer antibiotics under reductive activation conditions using either enzymes, sodium dithionite, catalytic hydrogenation or chromium (Il) perchlorate is examined, as is the alkylation of DNA. An intramolecular [3+2] cycloaddition strategy has been employed to synthesise the pyrrolo[I,2-aJ]indole nucleus for a wide range of cyclopropamitosenes, whereas the key step in the synthesis of pyrrolo[I ,2-a]indoles without the cyclopropane ring was a modified Wittig reaction. From the onset of the work it was important to investigate the role of the 7 -methoxy group. Hence a variety of cyclopropamitosenes or related pyrrolo[I,2-a]indoles were subjected to C-7 exchange reactions with either (i) other alkoxides or (ii) cyclic / acyclic amines. In this way, structural modification at C-7 can be related to the biological results. Biological and electrochemical data were recorded for the cyclopropamitosenes and related pyrrolo[I,2-a]indoles and correlated with their structures.
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Sun, Yiyang. "STATs signalling in human bladder cancer : potential chemopreventive role for indoles." Thesis, University of Leicester, 2007. http://hdl.handle.net/2381/29720.
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In patient tissues, STAT1, STAT3and STAT5 were observed in normal bladder epithelium, while expression of phosphorylated proteins was essentially absent. In contrast, phospho-STAT3 in superficial tumours and phospho-STAT1, 3 and 5 in muscle invasive tumours were present. Thus their increased expression, activation and nuclear localisation, may be associated with bladder tumour progression. Three epithelial bladder cancer lines (RT112, RT4, HT1376) had constitutive phospho-STAT5, while three mesenchymal lines (J82, T24, UMUC3) had activated STAT3. Specific knockdown of STAT3 in J82 cells increased STAT1 expression and phosphorylation. STAT1 and/or STAT3 knockdown led to inhibition of cell-matrix adhesion to fibronectin or collagen and suppression of cell migration. The dietary molecules, Indole-3-carbinol (I3C) (≥100microM) or 3, 3'-diindolylmethane (DIM) (≥50microM) induced apoptosis in J82 and RT112 cells by 48 hours. DIM-induced apoptosis in J82 cells was accompanied by downregulation of STAT1, 5a and 5b and inhibition of phospho-STAT1 and phospho-STAT3. In RT112 cells, DIM inhibited STAT5a, 5b and phospho-STAT5, but had no effect on STAT3. DIM (≥10microM) inhibited J82 cell adhesion to fibronectin and collagen, accompanied by decreased N-cadherin, P-cadherin and beta-catenin expression. Furthermore, DIM (1microM) was able to significantly decrease cell adhesion following STAT1 and/or STAT3 knockdown, suggesting inhibition of cell adhesion by DIM may involve the STAT pathway. Phosphorylated STATs may be a potential marker of invasiveness in human bladder cancer. Elucidation of the effects of indoles and DIM in particular, at a molecular level has given an insight as to how these dietary agents may be useful in the therapy and/or prevention of bladder tumours.
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Vogrig, Alexandre. "Synthèse et évaluation d'antalgiques originaux : les inhibiteurs de protéines à domaines PDZ." Phd thesis, Université Blaise Pascal - Clermont-Ferrand II, 2012. http://tel.archives-ouvertes.fr/tel-00803458.
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Les protéines à domaine PDZ, en très grand nombre dans le génome humain, sont impliquées dans des interactions protéine-protéine. Elles participent ainsi à véhiculer des signaux à l'origine de différentes pathologies (cancer, douleur....). L'interruption de l'interaction entre la protéine à domaine PDZ, PSD-95, et le récepteur de la sérotonine, 5-HT2A, entraîne une réduction de l'hyperalgie chez le rat neuropathique. Le développement de molécules capables d'inhiber cette interaction pourrait donc conduire à une nouvelle classe d'antalgiques.Nous avons réalisé, au cours de ces travaux, la synthèse de trois générations de ligands, comportant un noyau indolique, capables d'interagir avec le site S0, site très conservé des protéines à domaines PDZ. Dans un premier temps, nous avons préparé 15 biligands possédant un noyau indolique polysubstitué lié, via un espaceur de longueur variable (2 à 6 atomes de carbone), à différents acides aminés, dans le but d'interagir avec le site S1, montrant beaucoup de diversité en fonction du domaine. Nous avons ensuite, après une étude de relation structure/activité, développé deux autres générations d'indoles polysubstitués présentant notamment des substituants hydrophobes en position 5.Nous avons montré, par RMN HSQC 1H/15N et chromatographie d'affinité, que deux de ces composés sont des inhibiteurs de l'interaction PSD-95/5-HT2A et présentent de fortes interactions avec le site S0 de PSD-95. Ces molécules présentent également des propriétés antalgiques particulièrement intéressantes in vivo. Nous avons également déterminé, par RMN NOESY, la structure du complexe protéine/ligand pour ces deux composés. L'orientation d'une de ces molécules dans le site de la protéine nous permet d'envisager le développement d'une nouvelle génération d'indoles polysubstitués, pouvant interagir avec le site S1 de la protéine et permettant ainsi d'obtenir des inhibiteurs sélectifs de l'interaction PSD-95/5-HT2A.
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Adouama, Cherif. "Développement de méthodologies de SRN1 et de catalyse photoredox pour la synthèse d’indoles tétracycliques." Thesis, Lyon, 2018. http://www.theses.fr/2018LYSE1223/document.
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Le développement de nouvelles méthodologies de synthèse douces et soucieuses de l'environnement apparait de nos jours comme un véritable besoin. Dans ce contexte, la chimie radicalaire permet de réaliser une grande variété de réactions grâce à des initiations douces (électrochimique ou photochimique). Les indoles tétracycliques et les molécules gem-difluoroacylées étant présent dans de nombreux composé d'intérêt thérapeutique, sont des cibles pertinentes pour le développement de méthodes de synthèse radicalaire. Des indoles tétracycliques 3,4-fusionnés ont été synthétisés par Substitution Radicalaire Nucléophile Unimoléculaire (SRN1). Connue depuis les années 1960, la réaction SRN1 permet de réaliser des réactions de couplages entre un nucléophile et un accepteur d'électrons par un processus radicalaire. D'autre part, des indoles tétracycliques gem-difluoroacylés ont été synthétisés par cyclisation radicalaire tandem, initiée par catalyse électrochimique et photoredox. La catalyse photoredox, similaire à la catalyse électrochimique a connu un essor depuis sa redécouverte à la fin des années 2000. Elle est basée sur l'emploi d'un photocatalyseur qui peut être excité sous irradiation visible pour devenir oxydant ou réducteurThe development of new, soft and ecofriendly synthetic methodologies is today a real need. In this context, radical Chemistry allows to make a wide diversity of reactions thanks to soft initation steps (electrochemical or photochemical). Tetracyclic indoles and gem-difluoroacyles molecules, present in a lot of therapeutic compounds, appeared as relevant targets. 3,4-fused tetracyclic indoles, had been synthesized by Unimolecular Nucleophilic Radical Substitution (SRN1). Since the 1960s, SRN1 reaction allows coupling reactions between a nucleophilic species and a radical acceptor to be performed. On the other hand, gem-difluoroacyles tetracyclic indoles had been synthesized by tandem radical cyclisation initiated by electrochemical and photoredox catalysis. Since its rediscovery by the end of the 2000s, photoredox catalysis, similar to electrocatalysis, had seen an increasing interest. Photoredox catalysis is based on the use of a photocatalyst that become an oxidant or a reductant under visible irradiation
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Hirano, Kimio. "Direct Synthesis of Fused Indoles by Gold-Catalyzed Intramolecular Alkyne Cycloisomerization Cascade." 京都大学 (Kyoto University), 2012. http://hdl.handle.net/2433/159419.
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Slätt, Johnny. "Cyanoacetylation of indoles, pyrroles and amines, and synthetic uses of these products /." Stockholm, 2005. http://diss.kib.ki.se/2005/91-7140-269-1/.
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Haze, Olesya. "I. Persistent radicals for dynamic nuclear polarization : II. Synthesis of substituted indoles." Thesis, Massachusetts Institute of Technology, 2015. http://hdl.handle.net/1721.1/101454.
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Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2015.This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.
Cataloged from student-submitted PDF version of thesis.
Includes bibliographical references.
Part I: An brief introduction to dynamic nuclear polarization (DNP) is provided including a discussion of polarization mechanisms and development of new polarization methods in a historical context. Efficient synthesis of highly water-soluble BDPA derivatives that preserve the desirable DNP properties of BDPA and expand its application to aqueous systems is described. The narrow line radical applications in magnetic resonance spectroscopic imaging (MRSI) are investigated focusing on thermal mixing (TM) DNP of pyruvic acid. Design considerations and efforts toward the synthesis of bi- and multiradicals for Cross Effect (CE) DNP, and experiments performed with mixtures of radicals and covalently bound hetero-biradicals are reported. Part II: Indoles are important heterocycles because of their presence as common structural motifs in natural products and pharmaceutical candidates. Second generation Danheiser benzannulation-tandem cyclization approach was developed and applied toward the synthesis of highly substituted indoles. Substrate synthesis, benzannulation results and product elaboration are described.
by Olesya Haze.
Ph. D.
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Williams, Alice E. "Time resolved fluorescence and pH sensing studies of electropolymerised 5-substituted indoles." Thesis, University of Edinburgh, 2005. http://hdl.handle.net/1842/14666.
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In this thesis electropolymerised samples of the 5-cyanoindole and 5-bromoindole were studied. Steady state fluorescence and Time Correlated Single Photon Counting experiments were performed on solutions in ethanol of both types of polymer, and potentiometric experiments to ascertain the pH sensing ability of 5-cyanoindole solid films were carried out. The potential of rotating disc electrodes modified with thick (1.37μm) and thin (0.49μm) films 5-cyanoindole polymer were found to respond to changes in electrolyte pH linearly with a near-Nernstian slope, which is indicative of a promising pH sensing material. The response was independent of direction of pH change and sustainable over a time period of at least a week. The thin film shored promise as a good fast response pH sensor. Steady State (SS) fluorescence spectroscopy experiments carried out on solutions of electropolymerised 5-cyanoindole in ethanol at room temperature have shown that, when exciting at short wavelength the trimer chromophore gives the most intense emission at short wavelength, with no emission seen at longer wavelengths, and no noticeable difference between samples produced to produce trimer-rich and more extensively linked films. Exciting at longer wavelength a slight difference between the emission intensities of higher polymer and higher trimer content films was observed. Time Correlated Single Photon Counting (TCSPC) experiments were carried out at excitation wavelengths 360nm and 450nm and it was seen that the free trimer chromophore was the dominant contributor to the excited state population at all wavelengths. SS experiments were carried out on solutions of electropolymerised 5-bromoindole in ethanol and, consistent with previous work, it was seen that higher intensity of emission was seen in the polymeric region at longer emission wavelength. Additionally a marked difference was seen between higher and lower polymer content films.
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Denizot, Natacha. "Couplages oxydants entre indoles et phénols pour la synthèse de benzofuroindolines naturelles." Thesis, Université Paris-Saclay (ComUE), 2015. http://www.theses.fr/2015SACLS147/document.
Full textAbstract:
Le noyau benzofuro[2,3-b]indoline est une structure complexe que l’on retrouve dans différentes substances naturelles telles que l’azonazine, la voacalgine A, la bipleiophylline ou encore le diazonamide A. Ces produits naturels possèdent une activité biologique intéressante et plus particulièrement le diazonamide A avec un IC50 inférieur à 15ng/mL sur plusieurs lignées cellulaires cancéreuses. De plus, certaines de ces substances n’ont jamais été synthétisées à ce jour. Lors de la biogénèse de ces composés, il est supposé que le motif benzofuroindoline est créé par un couplage oxydant entre un indole et un phénol. Nous avons ainsi entrepris de développer différentes méthodologies de synthèse biomimétiques du motif benzofuroindoline. Inspiré par les biosynthèses de l’azonazine et du diazonamide A, nous avons développé une arylation diastéréodivergente du tryptophane par la tyrosine. Les diverses méthodologies de synthèse de benzofuroindolines existantes effectuant ce couplage ne permettent pas un contrôle stéréosélectif. Nous avons remédiés à ce problème en réalisant une réaction de Friedel-Crafts entre une tyrosine protégée et des exo- et endo-bromopyrroloindolines issues stéréosélectivement du tryptophane. Cette réaction procède avec rétention de configuration et nous permettent une synthèse diastéréodivergente de précurseurs potentiels du diazonamide et de l’azonazine. Une méthodologie générale de synthèse de benzofuroindolines par un couplage oxydant direct entre des indoles 2,3-disubstitués et des phénols a été développée. Cette réaction implique l’oxydation de l’indole par du N-iodosuccinimide. L’iodoindolénine intermédiaire réagit par action d’un sel d’argent, via une réaction de Friedel-Crafts avec le phénol pour donner la benzofuroindoline en une étape. Une bibliothèque de diverses benzofuroindolines a pu être obtenue par cette stratégie.Cette dernière méthodologie a été appliquée à la synthèse de modèles hexacycliques complexes de la voacalgine A et de la bipleiophylline à partir d’indoles apparentées à la pleiocarpamine que nous avons synthétisés. Une autre stratégie de synthèse du motif benzofuroindoline de la voacalgine A et de la bipleiophylline impliquant l’oxydation d’un catéchol en orthoquinone a également été étudiéeThe benzofuro[2,3-b]indoline core is a complex structure present in several natural products such as azonazine, voacalgine A, bipleiophylline and diazonamide A. These products possess an interesting biological activity and especially diazonamide A with an IC50 below 15ng/mL on different cancer cells lines. Some of these compounds have never been synthesize. It is postulated that the biogenesis of the benzofuroindolines natural products implies an oxidative coupling between indoles and phenols. Therefore, we wished to develop a bioinspired synthesis of benzofuroindoline core.Inspired by the biosynthesis of azonazine and diazonamide A, we developed an diastereodivergent arylation of tryptophan by tyrosine. The existing synthetic methodology of benzofuroindoline involving an oxidative coupling do not allow a stereoselective control. We solved this problem by doing a Friedel-Crafts reaction between a protected tyrosine and the exo-, and endo-bromopyrroloindolines obtained stereoselectively from tryptophan. This reaction witch proceeds with a retention of configuration allowed us to access selectively azonazine and diazonamide A precursors. A general methodology of benzofuroindoline synthesis by an oxidative coupling between 2,3-disubstituted indoles and phenols has then been developed. This reaction proceeds by oxidation of the indole with N-iodosuccinimide. The resulting iodoindoline was then engaged in a Friedel-Crafts reaction with a phenol in presence of a silver salt to form the desired benzofuroindoline in a one-pot operation. Through this method, a library of several benzofuroindolines has been created.This last methodology has been applied to the synthesis of complex hexacyclic voacalgine A and bipleiophylline analogs from pleiocarpamine-like indoles. Another strategy towards the voacalgine A and bipleiophylline benzofuroindoline core has also been studied and involves the oxidation of a catechol into an orthoquinone which can react with an indole
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Chaabouni, Slim. "Contribution à la chimie des cinnamates ortho-fonctionnalisés : Exploitation comme (1) précurseurs synthétiques d'hétérocycles, (2) antennes photoactivables de complexes d'ions lanthanides luminescents." Thesis, Toulouse 3, 2017. http://www.theses.fr/2017TOU30104/document.
Full textAbstract:
La chimie des cinnamates ortho-fonctionnalisés est particulièrement riche et variée, comme en témoigne le nombre important de méthodologies de synthèse reposant sur leur utilisation comme substrats précurseurs d'hétérocycles d'intérêt biologique. En effet, suivant la nature du groupe fonctionnel et les conditions opératoires, des substrats à base cinnamique ont déjà été exploités avec succès pour la construction d'un large panel de squelettes hétérocycliques, allant de systèmes cycliques à cinq chaînons (benzofurane, indole, ...) à des cycles à six chaînons (coumarine, quinolin(on)e, ...). Dans ce contexte, ma thèse avait pour objectif principal d'apporter une contribution à cette chimie propre aux cinnamates ortho-fonctionnalisés. Le premier objectif de mon travail a porté sur le développement de nouvelles méthodes de synthèse hétérocyclique employant des cinnamates ortho-fonctionnalisés comme précurseurs. D'une part, une méthode de synthèse de coumarines et de quinolones 3-trifluorométhylées a été mise au point à partir de d'ortho-hydroxy- et d'ortho-aminocinnamates. Une étude mécanistique a également été conduite et a permis de mettre évidence la nature radicalaire de la réaction de trifluorométhylation concernée. D'autre part, nous avons évalué avec succès le potentiel synthétique d'ortho-azidocinnamates pour la construction photoinduite d'indoles et de quinoléines. Le second objectif de mon travail a concerné la conception, la synthèse et l'évaluation photophysique/photochimique de nouvelles sondes photoactivables luminescentes à base d'ions lanthanides. Dans ce cas, le motif cinnamique a été installé sur un complexe de lanthanide non luminescent afin de jouer le rôle d'antenne photoactivable. Après une première étude ayant permis de prouver le concept, toute une série de composés a été préparée afin d'établir des relations structures-propriétés, relations qui nous ont finalement permis d'optimiser la performance de cette nouvelle classe de sondes luminescentes photoactivablesThe chemistry of ortho-functionalized cinnamates is particularly rich and varied, as evidenced by the large number of methods using them as building blocks for the synthesis of biologically-relevant heterocycles. In fact, depending on the nature of the functional group and the reaction conditions, various cinnamic-based substrates have already been successfully employed for the synthesis of a wide range of heterocyclic skeletons, ranging from five-membered ring systems (benzofuran, indole, ...) to six-membered rings (coumarin, quinolin(on)e, ...). In this context, the main goal of my thesis was to make a significant contribution to the chemistry peculiar to ortho-functionalized cinnamates. The first objective of my work dealt with the development of new methods for heterocyclic synthesis using ortho-functionalized cinnamates as building blocks. On one hand, a method for the regioselective synthesis of 3-trifluoromethylated coumarins and quinolones was elaborated starting from ortho-hydroxy- and ortho-aminocinnamates. The reaction mechanism of this trifluoromethylation reaction was further investigated and was found to involve radical participation. On the other hand, ortho-azidocinnamates proved suitable building blocks to achieve the construction of indoles and quinolines via a solvent-dependent photochemical process. The second objective of my work was devoted to the design, synthesis and photophysical/photochemical evaluation of new photoactivatable luminescent probes based on lanthanide ions. In this case, a non-luminescent lanthanide complex was equipped with a cinnamoyl residue in order to act as a photoactivatable sensitizer. A preliminary study allowed us to validate the concept "OFF/ON", and then a series of probes was prepared in order to establish relevant structure-property relationships, hence enabling the optimization of this novel class of photoactivatable luminescent probes