Дисертації з теми "Stereoselective reaction"
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Millet, Julien. "Approaches towards a stereoselective Nicholas reaction." Thesis, Kingston University, 2006. http://eprints.kingston.ac.uk/20379/.
Повний текст джерелаRutherford, Alistair Peter. "Stereoselective synthesis of #Beta#-hydroxycyclohexanones using the anionic oxy-cope rearrangement." Thesis, University of Glasgow, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.299981.
Повний текст джерелаLOPS, CARMINE. "Development of organocatalytic and stereoselective reactions." Doctoral thesis, Università degli Studi di Trieste, 2018. http://hdl.handle.net/11368/2918472.
Повний текст джерелаThomas, Jermaine D. O. "Highly regio and stereoselective hydroxy-directed Diels-Alder reaction." Thesis, University of Ottawa (Canada), 2002. http://hdl.handle.net/10393/6123.
Повний текст джерелаDawson, Graham John. "Studies on the stereoselective palladium-catalysed allylic substitution reaction." Thesis, Loughborough University, 1995. https://dspace.lboro.ac.uk/2134/31866.
Повний текст джерелаBeligny, Samuel Daniel Charles. "Stereoselective synthesis of tetrahydropyridines using the Diels-Alder reaction." Thesis, Imperial College London, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.414751.
Повний текст джерелаTakano, Toshiyuki. "SYNTHESIS OF CELLO-OLIGOSACCHARIDES -INFLUENCE OF SUBSTITUENT GROUPS ON STEREOSELECTIVE GLYCOSYLATION REACTION-." Kyoto University, 1990. http://hdl.handle.net/2433/78226.
Повний текст джерелаCresswell, Mark. "The stereoselective Pictet-Spengler reaction and studies towards the total synthesis of ajmaline." Thesis, Keele University, 2013. http://eprints.keele.ac.uk/3816/.
Повний текст джерелаHerlé, Bart. "Stereoselective Cyclopropanations via Gold(I)-Catalyzed Retro-Buchner Reactions." Doctoral thesis, Universitat Rovira i Virgili, 2017. http://hdl.handle.net/10803/454770.
Повний текст джерелаLa formación de carbenos bencílicos de oro(I) a partir de cicloheptatrienos sustituídos en la posición 7, a través de la reacción de retro-Buchner, ha surgido recientemente como una alternativa segura y versátil a la descomposición de diazocompuestos. Sin embargo, la formación de dichos carbenos tiene lugar a altas temperaturas, limitando su aplicación. El trabajo de esta tesis doctoral se dedicó a superar esta desventaja y a mejorar la versatilidad de la transformación. Los derivados de 1H-ciclopropa[l]fenantreno, que se asemejan al tautómero norcaradieno del cicloheptatrieno, se descomponen para dar lugar a carbenos libres mediante irradiación con luz. Se investigó la formación de carbenos de oro(I) con derivados de fenantreno, a través de la reacción de retro-Buchner. No obstante, no se encontró ninguna mejora significativa con respecto al uso de derivados de cicloheptatrieno. Por otro lado, la generación de carbenos alílicos de oro(I) a partir de 7-alquenil-cicloheptatrienos, tiene lugar a temperaturas significativamente más bajas. Dada esta observación, se desarrolló una reacción de ciclopropanación de olefinas para dar vinil-ciclopropanos y vinil-aminociclopropanos en buenos rendimientos y con elevada selectividad para el isómero cis. Los derivados de 7-alquenil-cicloheptatrieno son formados en un sólo paso a partir de aldehídos y cetonas utilizando un nuevo reactivo de tipo Julia-Kocienski. Adicionalmente, utilizando técnicas experimentales y computacionales, se estudiaron los mecanismos mediados por oro(I) de la reacción de retro-Buchner, de la ciclopropanación y de la reacción de epimerización de los vinilciclopropanos. Esto permitió el desarrollo de un modelo estereoquímico avanzado para las reacciones de ciclopropanación catalizadas por oro(I). El conocimiento aportado por los estudios mecanísticos y la síntesis mejorada de derivados de cicloheptatrieno, permitieron la síntesis de derivados de cicloheptatrieno más estéricamente congestionados, que dan lugar a carbenos de oro(I) a temperatura ambiente y son el punto de partida para el desarrollo de una ciclopropanción enantioselectiva de gran aplicación.
The formation of benzylic gold(I) carbenes from 7-substituted cycloheptatrienes via a retro-Buchner reaction has recently emerged as a safe and versatile alternative to decomposition of diazo compounds. However, the carbene formation takes places at high temperatures, which puts a limit on its application. The work in this thesis is dedicated to overcome this drawback and enhance the versatility of this transformation. Free carbenes can be generated from light-induced decomposition of 1H-cyclopropa[l]phenanthrenes, which bear great resemblance to the norcaradiene tautomer of cycloheptatriene. Therefore, the propensity to form gold(I) carbenes via the retro-Buchner reaction of phenanthrene derivatives was investigated, albeit without finding significant improvements over the cycloheptatriene derivatives. The formation of allylic gold(I) carbenes from 7-alkenyl cycloheptatrienes takes place at significantly lower temperatures. Based on this observation, a highly cis-selective olefin cyclopropanation reaction has been developed, affording vinylcyclopropanes and vinyl-aminocyclopropanes in moderate to good yield. The 7-alkenyl cycloheptatriene derivatives can be formed in a single step from aldehydes and ketones by a novel Julia-Kocienski reagent. The mechanisms of the gold(I)-mediated retro-Buchner, cyclopropanation, and epimerization reactions for vinylcyclopropanes have been studied experimentally and computationally, which led to the development of an advanced stereomodel for gold(I)-catalyzed cyclopropanation reactions. Owing to the mechanistic insights, and the improved strategy for the synthesis of cycloheptatriene reagents, a sterically encumbered cycloheptatriene derivative was developed, which allows the formation of gold(I) carbenes at room temperature, paving the way for a broad-scope enantioselective cyclopropanation reaction.
Peace, Simon. "The stereoselective nitro-Mannich reaction and its application towards the synthesis of vicinal diamines." Thesis, University of Sheffield, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.287661.
Повний текст джерелаHorsfall, L. R. "Stereoselective synthesis of pyrrolidinones via nitro-Mannich reaction : towards the synthesis of popolohuanone E." Thesis, University College London (University of London), 2011. http://discovery.ucl.ac.uk/1324535/.
Повний текст джерелаGilley, Cynthia Brooke. "New convertible isocyanides for the Ugi Reaction application to the stereoselective synthesis of omuralide /." Diss., Connect to a 24 p. preview or request complete full text in PDF format. Access restricted to UC campuses, 2008. http://wwwlib.umi.com/cr/ucsd/fullcit?p3328498.
Повний текст джерелаTitle from first page of PDF file (viewed November 5, 2008). Available via ProQuest Digital Dissertations. Vita. Includes bibliographical references.
Dogan, Sengul Dilem. "Regioselectivity In The Ene Reaction Of Singlet Oxygen With Cyclic Alkenes And Application Of Ene Reaction To Stereoselective Synthesis Of Carbaheptopyranose Derivatives." Phd thesis, METU, 2010. http://etd.lib.metu.edu.tr/upload/12612648/index.pdf.
Повний текст джерела-DL-galacto-heptopyranose (184) and 5a-carba-6-deoxy-&alpha
-DL-gulo-heptopyranose (185) have been prepared starting from cyclohexa-1,4-diene. The addition of dichloroketene to cyclohexa-1,4-diene followed by subsequent reductive elimination and Baeyer-Villiger oxidation formed the bicyclic lactone 188. Reduction of the lactone moiety followed by acetylation gave the diacetate 182b with cis-configuration. Introduction of additional acetate functionality into the molecule was achieved by singlet oxygen ene-reaction. The formed hydroperoxide 189 was reduced and then acetylated. The double bond in triacetate was further functionalized either by direct cis-hydroxylation using OsO4 or epoxidation followed by ring-opening reaction to give the hepto-pyranose derivatives 184 and 185.
Karak, Milandip. "A stereoselective vinylogous aldol reaction of tetronamides and the synthesis of rubrolides and beta- substituted butenolides." Universidade Federal de Viçosa, 2017. http://www.locus.ufv.br/handle/123456789/13425.
Повний текст джерелаMade available in DSpace on 2017-11-21T15:24:32Z (GMT). No. of bitstreams: 1 texto completo.pdf: 20136211 bytes, checksum: 27955f4b1fd7b5bdf978d63e7c835f6b (MD5) Previous issue date: 2017-01-27
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
Os butenolídeos, que apresentam em sua estrutura o núcleo lactona α, -insaturada, são encontrados em produtos naturais e não naturais com diversas propriedades biológicas. Devido à prevalência dos butenolídeos substituídos, muitos esforços têm sido direcionados para explorar metodologias eficientes para suas sínteses e transformações. Entre elas, o acesso estereosseletivo dos derivados de butenolídeos -substituídos utilizando o conceito de vinilogia, o qual envolve a formação de ligação carbono-carbono com um eletrófilo apropriado na posição do butenolídeo, tem provocado um interesse crescente. Portanto, esta tese apresenta uma reação aldólica viníloga estereosseleva (VAR) eficiente, simples, escalável e diretamente estereosseletiva de butenolídeos -amino-substituídos (tetronamidas) com aldeídos. Esta tese também descreve as sínteses totais de butenolídeos contendo metabólitos naturais marinhos rubrolídeos pela bromação altamente regiosseletiva de fase tardia a partir de intermediários apropriados. Além disso, a tese inclui uma desalogenação redutiva de butenolídeos α-halo- -substituídos sob condições suaves com rendimentos elevados e regiosseletivos. Uma introdução ao contexto geral, incluindo estratégias sintéticas versáteis, sínteses totais e propriedades biológicas dos butenolídeos substituídos estão documentadas na seção: Capítulo 1. Sendo seguida por uma ilustração dos métodos selecionados para a construção do núcleo de butenolídeos. São também discutidos os vários métodos para a preparação de alguns produtos naturais selecionados que possuem o núcleo de butenolídeo ou sintetizados a partir de butenolídeos que atuam como “building blocks”. Finalmente, foram descritos alguns butenolídeos sintéticos que são comercializados como medicamentos ou agroquimicos recentemente. Os resultados da VAR estereosseletiva de tetronamidas estão apresentatos no Capítulo 2. O procedimento descrito, simples e escalável, funciona bem com aldeídos aromáticos e alifáticos, proporcionando principalmente os adutos correspondentes de syn-aldol. Em muitos casos, estes últimos são obtidos isentos dos seus isômeros anti com rendimentos elevados. Foi também realizado um estudo computacional detalhado. Os estudos experimentais e computacionais sugerem que a diastereosseletividade observada surge através da interconversão do isômero anti-syn, através da reação reversível retro-aldólica. No Capítulo 3, as estruturas cristalinas de alguns produtos aldólicos de tetronamida com dois estereocentros foram descritos. Os compostos relacionados revelaram tendências conformacionais e supramoleculares com padrões de substituição do anel aromático/heteroaromático. Tais tendências foram racionalizadas com base nos perfis energéticos dos principais confôrmeros. A principal contribuição deste estudo refere-se ao controle sobre a conformação molecular de tetronamidas que apresentam várias ligações que permitem giros, além da elevada liberdade conformacional através do padrão de substituição de um único anel. As primeiras sínteses totais de produtos naturais marinhos, os rubrolídeos I e O e alguns de seus derivados não naturais são relatadas no Capítulo 4. Uma versátil estratégia de bromação na última etapa permitiu a funcionalização dos anéis aromáticos de maneira altamente regiosseletiva, permitindo o acesso rápido aos alvos, rubrolídeos, a partir de precursores comuns. Posteriormente, a cloração regiosselectiva foi também aplicada à preparação de análogos sintéticos biologicamente importantes a partir de precursores facilmente acessíveis. No Capítulo 5, foi relatado a desalogenação redutiva catalisada por paládio binário de butenolídeos α-halo- -substituídos. O procedimento sintético permitiu o acesso rápido aos butenolídeos substituídos sob condições suaves, com rendimentos elevados e excelente regiosseletividade. Além disso, uma nova proposta para a síntese dos rubrolídeos E, F e composto com a estrutura correspondente à descrita para 3"-bromorubrolídeo F de ocorrência natural utilizando este mesmo protocolo.
Butenolides are α, -unsaturated lactone and are found in many natural and unnatural products with diverse biological properties. Owing to the prevalence of the substituted butenolides, much effort has been directed towards developing efficient methodologies for their synthesis and transformations. Among them, stereoselective access of the -substituted butenolide derivatives by utilizing the concept of vinylogy, which usually involves the carbon– carbon formation with an appropriate electrophile at the -position of butenolides, has triggered increasing interest. This thesis presents an efficient, simple, scalable and direct stereoselective vinylogous aldol reaction (VAR) of -aminosubstituted butenolides (tetronamides) with aldehydes. In addition, this thesis also describes the total syntheses of butenolide core bearing marine natural metabolites, rubrolides by using a highly regioselective late-stage bromination from appropriate intermediates, and apprises a facile reductive dehalogenation of α-halo- -substituted butenolides. An introduction to the general background, including versatile synthetic strategies, total syntheses, and biological properties of substituted butenolides is documented in Chapter 1. It is followed by an illustration of selected methods for construction of the butenolide core. Also discussed are the various methods for preparation of some selected natural products which either possess a butenolide core or synthesized from butenolide building blocks. Finally, some synthetic butenolide derivatives are described which are recently marketed as either medicines or agrochemicals. The results of the stereoselective VAR of tetronamides are compiled in Chapter 2. The described procedure, is simple and scalable, works well with both aromatic and aliphatic aldehydes, and affords mainly the corresponding syn-aldol adducts. In many cases, the latter are obtained essentially free of their anti-isomers in high yields. A detailed computational study was also carried out to establish the reaction mechanism. The experimental and computational studies suggest that the observed diastereoselectivity arises through anti–syn isomer interconversion, enabled by an iterative retro-aldol/aldol reaction. In Chapter 3, the crystal structures of several tetronamide aldol products with two stereocenters are described. Those compounds revealed conformational and supramolecular trends with the substitution pattern of a side aromatic/ heteroaromatic ring. The major contribution of this study concerns the control over the molecular conformation of tetronamide aldolates bearing several rotatable bonds and the high conformational freedom through the substitution pattern of a single ring. The first total syntheses of the marine natural products rubrolides I and O and some of their unnatural congeners are reported in Chapter 4. A versatile late-stage bromination strategy allowed functionalization of the aromatic rings in a highly regioselective fashion, enabling rapid access to the target rubrolides from common precursors. Next, the regioselective chlorination was also applied to the preparation of biologically important synthetic analogous of rubrolides from easily accessible precursors. In Chapter 5, a binary palladium catalyzed reductive dehalogenation of α-halo- -substituted butenolides is documented. The synthetic procedure allowed rapid access to the -substituted butenolides under mild conditions with high yields and excellent regioselectivity. In addition, a protecting group free step-economical synthesis of rubrolides E, F and γ”-bromorubrolide F has been reported by employing this protocol.
Crossman, Julia Stephanie, and julia crossman@flinders edu au. "Biomimetic Approaches to the Synthesis of Polyketide Derived Marine Natural Products; (-)-Maurenone and the Spiculoic Acids." Flinders University. SoCPES, 2007. http://catalogue.flinders.edu.au./local/adt/public/adt-SFU20080212.134949.
Повний текст джерелаGuerrera, Cessandra. "Stereoselective Synthesis of alpha,alpha-Disubstituted Amino Acids Utilizing Porcine Liver Esterase and the Petasis Borono-Mannich Reaction." Thesis, Southern Connecticut State University, 2017. http://pqdtopen.proquest.com/#viewpdf?dispub=10283110.
Повний текст джерелаArginase is a manganese-containing enzyme that catalyzes the hydrolysis of L-arginine to yield L-ornithine and urea. It has been suggested that inhibition of arginase could be of therapeutic utility, and an arginase inhibitor is currently in phase I clinical trials for a variety of cancer subtypes. To date, the most promising inhibitors reported in the literature are α,α-disubstituted arginine analogs with a boronic acid warhead in place of the substrate guanidine group. However, the stereoselective approaches reported to date for this class of compounds have significant limitations and novel methods are needed. This research investigates two approaches: a route towards α,α-disubstituted amino acids via the enzyme-catalyzed desymmetrization of a meso diester and the utilization of the Petasis borono-Mannich reaction as an alternate enantioselective route for mono-substituted analogs.
Laws, Stephen William. "Total Synthesis of (+)-Malbrancheamide B Utilizing a Stereoselective Domino Reaction Sequence to Establish the Bicyclo[2.2]diazaoctane Core." W&M ScholarWorks, 2013. https://scholarworks.wm.edu/etd/1539626719.
Повний текст джерелаDanielsson, Jakob. "Stereoselective Nucleophilic Additions to Aldehydes and Synthesis of α-Amino-β- Hydroxy-Esters". Licentiate thesis, KTH, Organisk kemi, 2012. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-95467.
Повний текст джерелаQC 20120611
Penwell, Andrea J. "Sequential cycloadditions for the synthesis of taxoid mimics and stereoselective synthesis of tamoxifen analogues via a new carbomagnesiation-palladium coupling reaction." Thesis, University of Ottawa (Canada), 2003. http://hdl.handle.net/10393/26342.
Повний текст джерелаROUX, BRUNO. "Synthese regio et stereoselective d'acides alpha-amines par la reaction enique application a la preparation d'analogues de conformation restreinte de l'acide diaminopimelique." Paris 6, 1990. http://www.theses.fr/1990PA066676.
Повний текст джерелаDatta, Gopal K. "Heck Reactions with Aryl Chlorides : Studies of Regio- and Stereoselectivity." Doctoral thesis, Uppsala : Acta Universitatis Upsaliensis, 2008. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-9202.
Повний текст джерелаDuchesne, Jean-Pierre. "Nouvelle voie d'acces aux aldehydes terpeniques : synthese stereoselective des isomeres 11-trans du retinal a l'aide de sulfones." Paris 6, 1987. http://www.theses.fr/1987PA066347.
Повний текст джерелаBurke, Elizabeth Diane. "Stereoselective carbon-carbon bond forming reactions : improving the stereoselectivity of a catalytic homoaldol reaction and the development of a general method to access the [alpha]-quaternary carbon [beta]-hydroxy carbonyl motif." Thesis, McGill University, 2004. http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=85054.
Повний текст джерелаIn the second chapter, a general method for the asymmetric synthesis of alpha,alpha-disubstituted-beta-hydroxy carbonyl compounds is described. This methodology relies on the stereoselective formation of acyclic alpha,alpha-disubstituted amide enolates. These enolates were prepared using methodology developed in the Gleason laboratory. Transmetallation of the initially formed lithium enolate was necessary to achieve high relative and absolute product stereocontrol. The E- and Z-enolate isomers were investigated. The Z-enolate reacted with high stereocontrol, whereas the E-enolate was not able to provide the anti isomer selectively. An X-ray crystal structure confirmed the absolute configuration of the product.
Gallanti, M. "STEREOSELECTIVE SYNTHESIS OF A-AMINO ACIDS B-SUBSTITUTED WITH A 4,5-DIHYDROISOXAZOLE NUCLEUS AND OF TERTIARY AND QUATERNARY ALLYLSILANES." Doctoral thesis, Università degli Studi di Milano, 2012. http://hdl.handle.net/2434/168366.
Повний текст джерелаMRIDHA, MD MONIRUZZAMAN. "HIGHLY STEREOSELECTIVE ALDOL REACTION BY THE COMBINATION OF AMINOACID AND HYDROGEN BOND DONATING CATALYSTS IN WATER AND APPLICATION FOR CONCISE SYNTHESIS OF D-Lyxo-PHYTOSPHINGOSINE." Thesis, Uppsala universitet, Institutionen för kemi - BMC, 2012. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-328534.
Повний текст джерелаTiong, Erica. "Stereoselective formation of all carbon quaternary centers: synthesis of alpha,alpha-disubstituted beta-amino carbonyl compounds via the Mannich reaction and total synthesis of (-)-puraquinonic acid." Thesis, McGill University, 2011. http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=104585.
Повний текст джерелаUn auxiliaire chiral de type lactame thioglycolate bicyclique permettant la formation de carbones asymétriques quaternaires via une alkylation d'énolates fut développé précédemment par notre groupe de recherche. Cette méthode est remarquable puisqu'elle permet la génération stéréocontrôlée d'énolates d'amide alpha, alpha-disubstitués, sans égard à la différence stérique entre les substituants alpha Démontrant également une excellente discrimination faciale lors de l'approche de l'électrophile, ce protocole est maintenant devenu une méthode générale et pratique pour la préparation énantiosélective de carbones quaternaires par alkylation. Cette thèse rapporte l'application de cette méthode à la formation stéréosélective de composés beta-amino carbonyles alpha, alpha-disubstitués via la réaction de Mannich, ainsi que son utilisation dans la synthèse totale de l'acide (-)-puraquinonique.Les énolates alpha, alpha-disubstitués de lithium, générés de façon stéréosélective à partir de lactames thioglycolates bicycliques alpha, alpha-disubstituées, réagissent avec des imines benzènesulfoniques pour créer des acides beta-aminés avec grande efficacité et diastéréosélectivité. La réaction est générale pour une panoplie d'imines aromatiques, incluant celles comportant des substituants pauvres en électrons, riches en électrons, hétéroaromatiques, ainsi que des imines alpha, beta-insaturées. Les substituants alphades énolates d'amides peuvent être des groupements méthyle, éthyle, propyle benzyle et allyle. L'addition emploie un état de transition de type Zimmerman-Traxler où la géométrie de l'énolate contrôle le ratio d'addition anti/syn. Des méthodes de déprotection du groupe amino libérant des acides beta-aminés et des alcools sont décrites.Une courte synthèse de l'acide (-)-puraquinonique a été réalisée en utilisant l'auxiliaire chiral de type lactame thioglycolate bicyclique pour créer l'unique centre quaternaire présent tôt dans la séquence. Par la suite, un processus tandem fermeture de cycle par métathèse - cycloaddition de Diels-Alder produit un dihydroindene constituant le sytème bicyclique de l'acide puraquinonique. La quinone centrale est formée via une séquence comprenant un réarrangement de Curtius et une oxydation par le sel de Fremy. Lorsque la synthèse est complétée, l'auxiliaire est enlevé par une hydrolyse acide, révélant la fonctionnalité acide carboxylique nécessaire. La synthèse est complétée avec un rendement de 21 % à partir d'une lactame commercialement disponible, et ce, en 14 étapes. Cette synthèse représente donc une amélioration de 24 étapes par rapport à la synthèse asymétrique précédente.
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.
Alabdullah, Basil. "Stereoselective organoborate rearrangement reactions." Thesis, Cardiff University, 2015. http://orca.cf.ac.uk/75961/.
Повний текст джерелаPrasad, K. R. "Stereoselective carbonyl addition reactions." Thesis(Ph.D.), CSIR-National Chemical Laboratory, Pune, 1996. http://dspace.ncl.res.in:8080/xmlui/handle/20.500.12252/3010.
Повний текст джерелаNOGUE, DENISE. "Synthese regio et stereoselective d'heterocycles azotes via la reaction d'imino diels alder. Analyse conformationnelle de decahydroquinolein-4-ones et de piperidin-4-ones par correlation rmn #1h, m. M. Et rx." Paris 11, 1993. http://www.theses.fr/1993PA112254.
Повний текст джерелаMarín, Ferré Irene. "Stereoselective reactions in carbohydrate synthesis." Doctoral thesis, Universitat Rovira i Virgili, 2012. http://hdl.handle.net/10803/76720.
Повний текст джерелаThis thesis deals with two topics connected with carbohydrate chemistry. The first part presents epoxidation and dihydroxylation reactions of glycals using Mo-catalysts and m-chloroperbenzoic acid (MCPBA) towards the synthesis of manno oligosaccharides. The oxidation of glycals afforded in all cases the corresponding diols or glycosides, as a consequence of the in situ opening of the epoxides initially formed. Free hydroxyl groups were observed to direct the stereoselectivity of the epoxidation, and then manno derivatives were obtained from unprotected or partially protected glucals. The results using Mo-catalysts are among the best described for the catalytic epoxidation of glycals. The results using MCPBA were excellent, and this methodology was applied to the synthesis of orthogonally protected glycosyl donors. The second part is related to the synthesis of the cardiotonic digitoxin. Two different strategies were studied in order to obtain 2-deoxy-glycosides through olefination-cyclization-glycosylation reaction and using asymmetric synthesis.
Yan, Ni. "Stereoselective carbometallation reactions of cyclopropenes." Access to citation, abstract and download form provided by ProQuest Information and Learning Company; downloadable PDF file, 207 p, 2008. http://proquest.umi.com/pqdweb?did=1456289621&sid=2&Fmt=2&clientId=8331&RQT=309&VName=PQD.
Повний текст джерелаMaberly, T. R. "Stereoselective reactions of iron complexes." Thesis, University of Oxford, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.375266.
Повний текст джерелаPeverall, S. F. "Investigation of novel stereoselective reactions." Thesis, Swansea University, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.638517.
Повний текст джерелаMassolo, E. "NOVEL SYNTHETIC ORGANOCATALYTIC METHODOLOGIES." Doctoral thesis, Università degli Studi di Milano, 2015. http://hdl.handle.net/2434/330262.
Повний текст джерелаRIGUET, ERIC. "Reaction de couplage aryl-aryle, entre un organometallique et un bromure ou un chlorure aromatique, catalysee par un complexe du palladium ou du nickel. Cyclisation stereoselective utilisant un nouveau systeme catalytique mn/cu." Paris 6, 1997. http://www.theses.fr/1997PA066715.
Повний текст джерелаRAEPPEL, STEPHANE. "Synthese stereoselective de dienediynes tricycliques analogues structuraux du chromophore de la neocarzinostatine et approche synthetique du coeur de ce puissant anticancereux naturel. Nouvelle voie de synthese d'enediynes macrocycliques par la reaction s#nar." Université Louis Pasteur (Strasbourg) (1971-2008), 1998. http://www.theses.fr/1998STR13167.
Повний текст джерелаBender, Christoph. "Stereoselektive Synthese neuartiger 1,2-Dihydroisochinoline als Vorstufen für die Alkaloidsynthese." Doctoral thesis, Humboldt-Universität zu Berlin, Mathematisch-Naturwissenschaftliche Fakultät I, 2008. http://dx.doi.org/10.18452/15728.
Повний текст джерелаStarting points of the present work were stereoselective syntheses of Reissert compounds about chiral N-acylisoquinoliniumsalts. It was a matter of proving the configuration of the preserved products and of investigating synthesis potential. A purpose of this work was to develop continuing reactions for the synthesis of alkaloide-analogous substances. One succeeded in expanding the Reissert reaction with menthylchloroformat successfully to other heterocycles than isoquinoline. The acceptance a stereoselective course had to be corrected. The Reissert product could be alkylated with a big number of alkylhalides in 1 position. The Cyanogroup could be modified in two procedures. The treatment of the Reissert product and the alkylated compounds with acids, halogens and Grignard reagents led to different interesting cyclisations. One succeeded in extending the Reissert reaction to electronrich aromatic and heteroaromatic compounds and metal-organic reagents as nucleophiles. An asymmetrical C-C-bondformation with Zink-nucleophiles as well as Grignard compounds succeeded. 4-Bromine-substituted Mannich products could be transformed successfully in a Suzuki coupling to 4-arylsubstituted isoquinolineadducts. The hydrogenation of the enamindoublebond and the splitting off chirale auxiliary on two different ways succeeded. While addition reactions ran to the 1 position of 2-Menthyloxcarbonylisoquinoliniumsalts basically not stereoselectively, could be achieved by the application by protected Aminosäurefluoriden as chirale auxiliaries slide stereo selectivities up to 6:1. The application of the electronrich aromatics as nucleophiles led to Mannich products in good exploiting. Also the application of Grignard reagents as nucleophiles could be tested successfully. Herewith the first stereoselective addition from electronrich aromatics to cyclic iminiumsalts has succeeded.
PUGNAUD, SYLVIE. "Etude theorique de reactions stereoselectives : - reaction de diels-alder a demande inverse d'electrons - hydrogenation de cycloalcenes." Paris 6, 2000. http://www.theses.fr/2000PA066389.
Повний текст джерелаBlumenthal, Haiko. "Struktur und Reaktivität ausgewählter chiraler N-Acylaminohydroperoxide und -peroxide." Doctoral thesis, Humboldt-Universität zu Berlin, Mathematisch-Naturwissenschaftliche Fakultät I, 2009. http://dx.doi.org/10.18452/15868.
Повний текст джерелаStarting points of the present work were stereoselective syntheses of Reissert analogous N-acylaminohydroperoxides derived from chiral N-acylisochinoliniumsalts. Starting materials were isochinoline (and derivates), menthylchloroformiate and hydrogen peroxide. It was a matter of proving the configuration of the preserved products and of investigating the oxygen transfer potential. The second purpose of this work was to check the oxygen transfer potential of known diketopiperazinehydroperoxides likewise because they show the same N-acylaminohydroperoxide structure, however, up to now they were only examined scarcely. One succeeded by NMR investigations and comparison with similar reactions in disproving the acceptance of a stereoselective course. Furthermore it was shown that there are peroxides instead of hydroperoxides. We developed an in situ method to achieve with the given substances under addition of a metal catalyst like vanadium(V)triisopropylate and titanium(IV)tetraisopropylate an oxygen transfer to methylphenylsulfide. In dependence of the used isochinoline derivates a kinetic resolution was observed, so that a stereoselective sulfoxidation became possible. The most favorable result amounted to 51% sulfoxide with 73% enantiomeric excess. With a known diketopiperazinehydroperoxide methylphenylsulfide could be directly transfered into 62% sulfoxide with 32% enantiomeric excess. These are the first successful stereoselective sulfoxidations with chiral N-acylaminohydroperoxides.
Easton, R. J. C. "Stereoselective synthesis via iron acyl complexes." Thesis, University of Oxford, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.379991.
Повний текст джерелаSmith, Elin Hopcyn. "Stereoselective Hex-5-enyl radical cyclisations." Thesis, University of Southampton, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.259644.
Повний текст джерелаXie, Jianing. "Advancing Pd-catalyzed Stereoselective Allylic Substitution Reactions." Doctoral thesis, Universitat Rovira i Virgili, 2020. http://hdl.handle.net/10803/670221.
Повний текст джерелаEsta tesis doctoral se centra principalmente en el desarrollo de nuevos métodos catalíticos (dominó) basados en la sustitución alílica catalizada por Pd para la síntesis estereoselectiva de pequeñas moléculas funcionales y heterociclos utilizando un diseño detallado de ligandos y sustratos. Esta tesis está organizada en cinco capítulos: el primer capítulo es una introducción general sobre los aspectos básicos de la química alílica. El segundo capítulo ilustra el primer método general para la preparación de éteres arílicos alílicos terciarios enantioenriquecidos mediante una eterificación regio- y enantio-selectiva catalizada por Pd de los VCCs en presencia de nucleófilos fenólicos. La regioselectividad de la reacción puede ajustarse selectivamente al producto lineal Z cambiando el ligando fosforamidito a un ligando monofosfina, demostrando así el papel crucial del diseño adecuado del ligando. El tercer capítulo describe el diseño de un nuevo alcohol alílico terciario equipado con un grupo carboxilo, que se utiliza en primer lugar para la síntesis de γ-lactamas α,β-insaturadas mediante una aminación alílica estereoselectiva catalizada por Pd, seguido por un proceso de ciclación intramolecular. Los estudios mecanisticos sugieren que el grupo carboxilo es crucial para esta transformación y actúa como un grupo funcional activador y estereodirector. El cuarto capítulo presenta un enfoque estereodivergente controlado por el ligando para la síntesis de γ-aminoácidos con configuración Z o E derivados de alcoholes alílicos terciarios y aminas secundarias. Los resultados experimentales destacan el papel crucial del ligando de soporte y el ángulo de mordedura de la difosfina. El quinto capítulo informa sobre un método general para la síntesis de caprolactamas insaturadas sustituidas a través de un proceso de aminación / ciclación en cascada utilizando vinil γ-lactonas como sustratos mediante el uso de un ligando fosforamidito recientemente desarrollado. Finalmente, se extrae una conclusión general para cada capítulo y también se discute la aplicación potencial de estas metodologías desarrolladas.
This doctoral thesis is mainly focused on the development of novel catalytic (domino) synthesis methods based on Pd-catalyzed allylic substitution for the stereoselective synthesis of functional small molecules and heterocycles utilizing a detailed ligand engineering and substrate design. The scope of this thesis is organized into five chapters: the first chapter is a general introduction on the regular aspects of allylic chemistry. The second chapter illustrates the first general method for the preparation of enantioenriched tertiary allylic aryl ethers through a Pd-catalyzed regio- and enantio-selective etherification of VCCs in the presence of phenolic nucleophiles. The regioselectivity of the reaction can be finely tuned to the Z-selective linear product by switching the phosphoramidite ligand to a monophosphine ligand, thus proving the crucial role of proper ligand engineering. The third chapter describes a newly designed tertiary allylic alcohol equipped with a carboxyl group, which is firstly used for α,β-unsaturated γ-lactams synthesis through Pd-catalyzed stereoselective allylic amination and intramolecular cyclization process. Mechanistic studies suggest that the carboxyl group is crucial for this transformation, and acts as an activating and stereodirecting functional group. The fourth chapter presents a ligand-controlled stereodivergent approach for the synthesis of either Z or E-configured γ-amino acids derived from tertiary allylic alcohols and secondary amines. The experimental results highlight the crucial role of the supporting ligand and the diphosphine bite angle. The fifth chapter reports a general method for substituted unsaturated caprolactam synthesis through a cascade amination/cyclization process using vinyl γ-lactones as substrate by using a newly developed phosphoramidite ligand. Finally, a general conclusion for each chapter is given and potential applications for these developed methodologies are also discussed.
Baar, Cliff Robert. "Stereoselective reactions of organoplatinum and organopalladium complexes." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2000. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape2/PQDD_0019/NQ58394.pdf.
Повний текст джерелаJoensuu, Pekka Matias. "Development of catalytic stereoselective reductive aldol reactions." Thesis, University of Edinburgh, 2008. http://hdl.handle.net/1842/2576.
Повний текст джерелаGoodfellow, Craig L. "Stereoselective reactions of arene chromium tricarbonyl complexes." Thesis, University of Oxford, 1989. http://ora.ox.ac.uk/objects/uuid:e2833156-aec2-42e5-b835-e9ddca4fa27c.
Повний текст джерелаKaiser, Delene Anne. "Stereoselective reactions of 16-Methylene 19-Norsteroids." Master's thesis, University of Cape Town, 1991. http://hdl.handle.net/11427/22136.
Повний текст джерелаGuiteras, Capdevila Montserrat <1980>. "Development of Organocatalytic stereoselective SN1 type reactions." Doctoral thesis, Alma Mater Studiorum - Università di Bologna, 2012. http://amsdottorato.unibo.it/4370/1/Guitera_Capdevila_Montse_tesi.pdf.
Повний текст джерелаLa proposta della mia tesi è stato lo studio stereoselettiva di α-alchilazione attraverso la reazione di tipo SN1. SN1 reazione tipo comporta un stabilizzato e reattivo carbocatione intermedio Prendendo vantaggi della stabilità dei carbocationi particolari, l'uso di carbocationi in reazioni selettive è stato importante. In questo lavoro è stato necessario conoscere la stabilità e reattività dei carbocationi. E il lavoro di Mayr gruppo ha contribuito a razionalizzare il comportamento e reattività tra i carbocationi e nucleofili con l'uso della scala Mayr di reattività. L'uso di alcool ai eseguito i carbocationi stabili e reattive sono state la chiave nella mia tesi. La sostituzione nucleofila diretta di alcoli è stata portata cruciale nel campo della sintesi organica, poiché offrono un'ampia gamma di intermedi per la sintesi di prodotti naturali e di sintesi farmaceutica. In particolare il catalizzatore sostituzione nucleofila diretta di alcoli rappresenta una nuova metodologia per la preparazione di una varietà di derivati, e l'acqua come unico sottoprodotto nella reazione. Il controllo stereochimica del legame CH trasformazione in legame C-C stereogenico adiacente al carbonile funzionalizzata è stata studiata per la catalisi asimmetrica. E il campo dell'organocatalisi ha introdotto l'uso di piccola molecola organica come catalizzatore per trasformazioni stereoselettive. L'unione dell'organocatalisi questi due concetti e la scala Mayr, la mia tesi ha sviluppato un nuovo approccio per la α-alchilazione di aldeidi e chetoni, attraverso reazione di tipo SN1
Guiteras, Capdevila Montserrat <1980>. "Development of Organocatalytic stereoselective SN1 type reactions." Doctoral thesis, Alma Mater Studiorum - Università di Bologna, 2012. http://amsdottorato.unibo.it/4370/.
Повний текст джерелаLa proposta della mia tesi è stato lo studio stereoselettiva di α-alchilazione attraverso la reazione di tipo SN1. SN1 reazione tipo comporta un stabilizzato e reattivo carbocatione intermedio Prendendo vantaggi della stabilità dei carbocationi particolari, l'uso di carbocationi in reazioni selettive è stato importante. In questo lavoro è stato necessario conoscere la stabilità e reattività dei carbocationi. E il lavoro di Mayr gruppo ha contribuito a razionalizzare il comportamento e reattività tra i carbocationi e nucleofili con l'uso della scala Mayr di reattività. L'uso di alcool ai eseguito i carbocationi stabili e reattive sono state la chiave nella mia tesi. La sostituzione nucleofila diretta di alcoli è stata portata cruciale nel campo della sintesi organica, poiché offrono un'ampia gamma di intermedi per la sintesi di prodotti naturali e di sintesi farmaceutica. In particolare il catalizzatore sostituzione nucleofila diretta di alcoli rappresenta una nuova metodologia per la preparazione di una varietà di derivati, e l'acqua come unico sottoprodotto nella reazione. Il controllo stereochimica del legame CH trasformazione in legame C-C stereogenico adiacente al carbonile funzionalizzata è stata studiata per la catalisi asimmetrica. E il campo dell'organocatalisi ha introdotto l'uso di piccola molecola organica come catalizzatore per trasformazioni stereoselettive. L'unione dell'organocatalisi questi due concetti e la scala Mayr, la mia tesi ha sviluppato un nuovo approccio per la α-alchilazione di aldeidi e chetoni, attraverso reazione di tipo SN1
Porta, R. "STEREOSELECTIVE CATALYTIC REACTIONS UNDER CONTINUOUS FLOW CONDITIONS." Doctoral thesis, Università degli Studi di Milano, 2017. http://hdl.handle.net/2434/479336.
Повний текст джерела