New reactivity of p-quinols and p-quinones. Synthesis and properties of photoactivatable pyrazolequinones

Tesis doctoral inédita leída en la Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Química Orgánica. Fecha de lectura: 04-12-2019

Detalhes bibliográficos
Autor: Ortiz Rojano, Laura
Tipo de documento: tese
Data de publicação:2019
País:España
Recursos:Universidad Autónoma de Madrid
Repositório:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglês
OAI Identifier:oai:repositorio.uam.es:10486/690595
Acesso em linha:http://hdl.handle.net/10486/690595
Access Level:Acceso aberto
Palavra-chave:Compuestos orgánicos - Síntesis - Tesis doctorales
Química
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spelling New reactivity of p-quinols and p-quinones. Synthesis and properties of photoactivatable pyrazolequinonesOrtiz Rojano, LauraCompuestos orgánicos - Síntesis - Tesis doctoralesQuímicaTesis doctoral inédita leída en la Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Química Orgánica. Fecha de lectura: 04-12-2019Esta tesis tiene embargado el acceso al texto completo hasta el 04-06-2021The present doctoral thesis has studied different reactivities and properties of p-quinols and pquinones. In the first part of this investigation, it has been carried out the study of a new reactivity of p-quinols in the enantioselective Friedel-Crafts reaction with different heteroaromatic derivatives catalyzed by a BINOL phosphoric acid derivative. As result, it has been achieved for the first time the Friedel-Crafts alkylation compounds with moderate enantioselectivities and excellent diastereoselectivities and therefore accomplished the challenging task of p-quinol desymmetrization. Furthermore, the work has been complemented with computational studies in order to determine the mechanism of the reaction and the absolute configuration of the Friedel-crafts alkylation compounds. The second chapter of this Ph. D. work focusses on the reactivity of quinones with aketoacids. In particular, it has been revealed a double reactivity of the phenylpyruvic acid with naphthoquinone, acting both as a nucleophile as an acylation agent through a domino process that leads to a new synthesis of 3,3-disubstituted naphtho[1,2-b]furan-2(3H)-ones through two Michael type addition reactions followed by a decarboxylative process and an intramolecular lactonization. The optimized reaction was carried out using a wide variety of a-ketoacids and differently substituted quinones. In the first part of the third chapter, another new reactivity of p-quinones has been exhibited, in this case, as dipolarophiles in photoinduced 1,3-dipolar cycloadditions using tetrazoles as precursors of nitrilimine dipoles. This methodology has allowed the synthesis of three different families of pyrazolequinones. After optimization of the reaction conditions a wide scope of both tetrazoles and different benzoindazole-, indazole- or pyrazoleindazolediones has been obtained. Furthermore, in the second part of the third chapter, it has been carried out a detailed study of the photoactivatable properties of the newly synthetized heterocyclic quinones. The spectroscopic study embracing absorption and emission has shown that these compounds absorbs in the blue region and present fluorescence in the orange red one. The electrochemical study performed recording cyclic and square wave voltammetries, together with the estimation of the excited state potentials, has revealed that this new family of quinones significantly increases their oxidizing power by irradiation with blue light, which also triggers singlet oxygen generation. Finally, a study of the biological properties of a selection of quinones was carried out, including cytotoxicity studies in darkness and under irradiation with blue light, as well as studies of subcellular localizationEl trabajo se ha llevado a cabo gracias a la financiación del Ministerio de Economía y Competitividad (MINECO) (Proyectos: CTQ2014-53894-R y CTQ2017-85454-C2-2-P) y a la obtención de una Beca de Formación para Personal Investigador (FPI) del Ministerio de Economía y Competitividad (MINECO).Carreño García, CarmenRibagorda Lobera, MaríaDepartamento de Química OrgánicaFacultad de Ciencias20192019-12-04doctoral thesishttp://purl.org/coar/resource_type/c_db06NAhttp://purl.org/coar/version/c_be7fb7dd8ff6fe43info:eu-repo/semantics/doctoralThesisapplication/pdfhttp://hdl.handle.net/10486/690595reponame:Biblos-e Archivo. Repositorio Institucional de la UAMinstname:Universidad Autónoma de MadridInglésengopen accesshttp://purl.org/coar/access_right/c_abf2info:eu-repo/semantics/openAccessoai:repositorio.uam.es:10486/6905952026-06-23T12:46:27Z
dc.title.none.fl_str_mv New reactivity of p-quinols and p-quinones. Synthesis and properties of photoactivatable pyrazolequinones
title New reactivity of p-quinols and p-quinones. Synthesis and properties of photoactivatable pyrazolequinones
spellingShingle New reactivity of p-quinols and p-quinones. Synthesis and properties of photoactivatable pyrazolequinones
Ortiz Rojano, Laura
Compuestos orgánicos - Síntesis - Tesis doctorales
Química
title_short New reactivity of p-quinols and p-quinones. Synthesis and properties of photoactivatable pyrazolequinones
title_full New reactivity of p-quinols and p-quinones. Synthesis and properties of photoactivatable pyrazolequinones
title_fullStr New reactivity of p-quinols and p-quinones. Synthesis and properties of photoactivatable pyrazolequinones
title_full_unstemmed New reactivity of p-quinols and p-quinones. Synthesis and properties of photoactivatable pyrazolequinones
title_sort New reactivity of p-quinols and p-quinones. Synthesis and properties of photoactivatable pyrazolequinones
dc.creator.none.fl_str_mv Ortiz Rojano, Laura
author Ortiz Rojano, Laura
author_facet Ortiz Rojano, Laura
author_role author
dc.contributor.none.fl_str_mv Carreño García, Carmen
Ribagorda Lobera, María
Departamento de Química Orgánica
Facultad de Ciencias
dc.subject.none.fl_str_mv Compuestos orgánicos - Síntesis - Tesis doctorales
Química
topic Compuestos orgánicos - Síntesis - Tesis doctorales
Química
description Tesis doctoral inédita leída en la Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Química Orgánica. Fecha de lectura: 04-12-2019
publishDate 2019
dc.date.none.fl_str_mv 2019
2019-12-04
dc.type.none.fl_str_mv doctoral thesis
http://purl.org/coar/resource_type/c_db06
NA
http://purl.org/coar/version/c_be7fb7dd8ff6fe43
dc.type.openaire.fl_str_mv info:eu-repo/semantics/doctoralThesis
format doctoralThesis
dc.identifier.none.fl_str_mv http://hdl.handle.net/10486/690595
url http://hdl.handle.net/10486/690595
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:Biblos-e Archivo. Repositorio Institucional de la UAM
instname:Universidad Autónoma de Madrid
instname_str Universidad Autónoma de Madrid
reponame_str Biblos-e Archivo. Repositorio Institucional de la UAM
collection Biblos-e Archivo. Repositorio Institucional de la UAM
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.300724

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