Stereoselective reactions in carbohydrate synthesis

This 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...

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Detalhes bibliográficos
Autor: Marín Ferré, Irene
Tipo de documento: tese
Estado:Versão publicada
Data de publicação:2012
País:España
Recursos:Universitat Rovira i virgili (URV)
Repositório:Repositori Institucional de la Universitat Rovira i Virgili
OAI Identifier:oai:urv.cat:TDX:1036
Acesso em linha:https://hdl.handle.net/20.500.11797/TDX1036
http://hdl.handle.net/10803/76720
Access Level:Acceso aberto
Palavra-chave:547 - Química orgànica
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spelling Stereoselective reactions in carbohydrate synthesisMarín Ferré, Irene547 - Química orgànicaThis 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.La Tesis que se presenta trata sobre el desarrollo de nuevos métodos selectivos de síntesis de carbohidratos. En la primera parte de la tesis se estudió la epoxidación de glicales utilizando catalizadores de Mo y ácido meta-cloroperbenzoico (MCPBA), en relación con la obtención de mano-oligosacáridos. En todos los casos estudiados, el epóxido formado se abría in situ para dar lugar al correspondiente diol o glicósido. Se observó un efecto director por parte de los hidroxilos libres, lo que permitía obtener derivados de manosa a partir de glucosa. En el caso del Mo, los resultados figuran entre los mejores descritos para epoxidación de glicales con catalizadores. Los resultados con MCPBA fueron excelentes, aplicándose este último procedimiento a la síntesis ortogonal de dadores de glicosilo. En la segunda parte, relacionado con la síntesis del cardiotónico digitoxina, se estudiaron dos metodologías sintéticas para obtener 2-desoxi-glicósidos mediante reacción de olefinación-ciclación-glicosilación y a través de síntesis asimétrica.Universitat Rovira i Virgili Departament de Química Analítica i Química OrgànicaUniversitat Rovira i Virgili.2012info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdf213 p.https://hdl.handle.net/20.500.11797/TDX1036http://hdl.handle.net/10803/76720reponame:Repositori Institucional de la Universitat Rovira i Virgiliinstname:Universitat Rovira i virgili (URV)Inglésinfo:eu-repo/semantics/openAccessADVERTIMENT. L'accés als continguts d'aquesta tesi doctoral i la seva utilització ha de respectar els drets de la persona autora. Pot ser utilitzada per a consulta o estudi personal, així com en activitats o materials d'investigació i docència en els termes establerts a l'art. 32 del Text Refós de la Llei de Propietat Intel·lectual (RDL 1/1996). Per altres utilitzacions es requereix l'autorització prèvia i expressa de la persona autora. En qualsevol cas, en la utilització dels seus continguts caldrà  indicar de forma clara el nom i cognoms de la persona autora i el títol de la tesi doctoral. No s'autoritza la seva reproducció o altres formes d'explotació efectuades amb finalitats de lucre ni la seva comunicació pública des d'un lloc aliè al repositori institucional de la Universitat Rovira i Virgili. Tampoc s'autoritza la presentació del seu contingut en una finestra o marc aliè a aquest repositori (framing). Aquesta reserva de drets afecta tant als continguts de la tesi com als seus resums i índexs.oai:urv.cat:TDX:10362026-06-23T12:42:27Z
dc.title.none.fl_str_mv Stereoselective reactions in carbohydrate synthesis
title Stereoselective reactions in carbohydrate synthesis
spellingShingle Stereoselective reactions in carbohydrate synthesis
Marín Ferré, Irene
547 - Química orgànica
title_short Stereoselective reactions in carbohydrate synthesis
title_full Stereoselective reactions in carbohydrate synthesis
title_fullStr Stereoselective reactions in carbohydrate synthesis
title_full_unstemmed Stereoselective reactions in carbohydrate synthesis
title_sort Stereoselective reactions in carbohydrate synthesis
dc.creator.none.fl_str_mv Marín Ferré, Irene
author Marín Ferré, Irene
author_facet Marín Ferré, Irene
author_role author
dc.contributor.none.fl_str_mv Departament de Química Analítica i Química Orgànica
Universitat Rovira i Virgili.
dc.subject.none.fl_str_mv 547 - Química orgànica
topic 547 - Química orgànica
description This 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.
publishDate 2012
dc.date.none.fl_str_mv 2012
dc.type.none.fl_str_mv info:eu-repo/semantics/publishedVersion
info:eu-repo/semantics/doctoralThesis
format doctoralThesis
status_str publishedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/20.500.11797/TDX1036
http://hdl.handle.net/10803/76720
url https://hdl.handle.net/20.500.11797/TDX1036
http://hdl.handle.net/10803/76720
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
213 p.
dc.publisher.none.fl_str_mv Universitat Rovira i Virgili
publisher.none.fl_str_mv Universitat Rovira i Virgili
dc.source.none.fl_str_mv reponame:Repositori Institucional de la Universitat Rovira i Virgili
instname:Universitat Rovira i virgili (URV)
instname_str Universitat Rovira i virgili (URV)
reponame_str Repositori Institucional de la Universitat Rovira i Virgili
collection Repositori Institucional de la Universitat Rovira i Virgili
repository.name.fl_str_mv
repository.mail.fl_str_mv
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