Synthesis and Study of Functionalized Porphyrins as Organophotoredox Catalysts
[eng] Visible-light photocatalysis is currently one of the hottest research areas in organic chemistry, due to the possibility that offers to form C-C and C-Het bonds in a green, non-toxic and efficient way. Although visible-light photocatalysis has been the object of unabated interest in the last f...
| Autor: | |
|---|---|
| Tipo de recurso: | tesis doctoral |
| Estado: | Versión publicada |
| Fecha de publicación: | 2022 |
| País: | España |
| Institución: | Universidad de Barcelona |
| Repositorio: | Dipòsit Digital de la UB |
| OAI Identifier: | oai:diposit.ub.edu:2445/192125 |
| Acceso en línea: | https://hdl.handle.net/2445/192125 http://hdl.handle.net/10803/687402 |
| Access Level: | acceso abierto |
| Palabra clave: | Química orgànica Catàlisi asimètrica Porfirines Organic chemistry Enantioselective catalysis Porphyrins |
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Synthesis and Study of Functionalized Porphyrins as Organophotoredox Catalysts |
| title |
Synthesis and Study of Functionalized Porphyrins as Organophotoredox Catalysts |
| spellingShingle |
Synthesis and Study of Functionalized Porphyrins as Organophotoredox Catalysts Torres Yeste, Pol Química orgànica Catàlisi asimètrica Porfirines Organic chemistry Enantioselective catalysis Porphyrins |
| title_short |
Synthesis and Study of Functionalized Porphyrins as Organophotoredox Catalysts |
| title_full |
Synthesis and Study of Functionalized Porphyrins as Organophotoredox Catalysts |
| title_fullStr |
Synthesis and Study of Functionalized Porphyrins as Organophotoredox Catalysts |
| title_full_unstemmed |
Synthesis and Study of Functionalized Porphyrins as Organophotoredox Catalysts |
| title_sort |
Synthesis and Study of Functionalized Porphyrins as Organophotoredox Catalysts |
| dc.creator.none.fl_str_mv |
Torres Yeste, Pol |
| author |
Torres Yeste, Pol |
| author_facet |
Torres Yeste, Pol |
| author_role |
author |
| dc.contributor.none.fl_str_mv |
Moyano i Baldoire, Albert Universitat de Barcelona. Departament de Química Inorgànica i Orgànica |
| dc.subject.none.fl_str_mv |
Química orgànica Catàlisi asimètrica Porfirines Organic chemistry Enantioselective catalysis Porphyrins |
| topic |
Química orgànica Catàlisi asimètrica Porfirines Organic chemistry Enantioselective catalysis Porphyrins |
| description |
[eng] Visible-light photocatalysis is currently one of the hottest research areas in organic chemistry, due to the possibility that offers to form C-C and C-Het bonds in a green, non-toxic and efficient way. Although visible-light photocatalysis has been the object of unabated interest in the last few years, the development of catalytic enantioselective light-driven processes is still an extremely challenging task. That is why a large number of research groups have dedicated their efforts to trying to make photocatalysis coexist with asymmetric catalysis. In this sense, asymmetric photocatalytic transformations have been successfully achieved by using two different methodologies; the so-called dual catalysis, where photocatalysts are combined with chiral co- catalysts that work in a tandem fashion for a single chemical reaction, and the so-called, bifunctional catalysis, where a single catalyst perform both photo- and organo-catalysis, being the latter the less explored methodology due to the complexity of finding and synthesizing a suitable bifunctional catalyst. In the last years, porphyrins, such as meso-tetraphenylporphyrin (TPP), have showed up as a suitable organic photocatalyst for the development of new methodologies for the construction of new C-C and C-Het bonds, thus avoiding the use of metal-based photocatalysts. In this field, some recent works show their capacity for acting as photoredox catalysts in the racemic organophotocatalytic alpha-alkylation reaction of aldehydes with diazoacetates, being unexplored their asymmetric version. In the light of our interest of new catalytic applications of porphyrins, we were particularly attracted by these reports. This present work is focused on the study of the asymmetric Diels-Alder cycloaddition in both thermal and photochemical conditions and development of a practical enantioselective version of the organophotocatalytic alpha-alkylation of aldehydes with diazoacetates. Moreover, we present different porphyrin-based bifunctional photoaminocatalysts based on the combination of both an organocatalyst (chiral secondary amines) and a photocatalyst (porphyrin). |
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2022 |
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2022 |
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info:eu-repo/semantics/doctoralThesis info:eu-repo/semantics/publishedVersion |
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doctoralThesis |
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publishedVersion |
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https://hdl.handle.net/2445/192125 http://hdl.handle.net/10803/687402 |
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https://hdl.handle.net/2445/192125 http://hdl.handle.net/10803/687402 |
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Inglés |
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Inglés |
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(c) Torres Yeste, Pol, 2023 info:eu-repo/semantics/openAccess |
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(c) Torres Yeste, Pol, 2023 |
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openAccess |
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application/pdf |
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Universitat de Barcelona |
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Universitat de Barcelona |
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Tesis Doctorals - Departament - Química Inorgànica i Orgànica reponame:Dipòsit Digital de la UB instname:Universidad de Barcelona |
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Universidad de Barcelona |
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Dipòsit Digital de la UB |
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Dipòsit Digital de la UB |
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1869411818405888000 |
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Synthesis and Study of Functionalized Porphyrins as Organophotoredox CatalystsTorres Yeste, PolQuímica orgànicaCatàlisi asimètricaPorfirinesOrganic chemistryEnantioselective catalysisPorphyrins[eng] Visible-light photocatalysis is currently one of the hottest research areas in organic chemistry, due to the possibility that offers to form C-C and C-Het bonds in a green, non-toxic and efficient way. Although visible-light photocatalysis has been the object of unabated interest in the last few years, the development of catalytic enantioselective light-driven processes is still an extremely challenging task. That is why a large number of research groups have dedicated their efforts to trying to make photocatalysis coexist with asymmetric catalysis. In this sense, asymmetric photocatalytic transformations have been successfully achieved by using two different methodologies; the so-called dual catalysis, where photocatalysts are combined with chiral co- catalysts that work in a tandem fashion for a single chemical reaction, and the so-called, bifunctional catalysis, where a single catalyst perform both photo- and organo-catalysis, being the latter the less explored methodology due to the complexity of finding and synthesizing a suitable bifunctional catalyst. In the last years, porphyrins, such as meso-tetraphenylporphyrin (TPP), have showed up as a suitable organic photocatalyst for the development of new methodologies for the construction of new C-C and C-Het bonds, thus avoiding the use of metal-based photocatalysts. In this field, some recent works show their capacity for acting as photoredox catalysts in the racemic organophotocatalytic alpha-alkylation reaction of aldehydes with diazoacetates, being unexplored their asymmetric version. In the light of our interest of new catalytic applications of porphyrins, we were particularly attracted by these reports. This present work is focused on the study of the asymmetric Diels-Alder cycloaddition in both thermal and photochemical conditions and development of a practical enantioselective version of the organophotocatalytic alpha-alkylation of aldehydes with diazoacetates. Moreover, we present different porphyrin-based bifunctional photoaminocatalysts based on the combination of both an organocatalyst (chiral secondary amines) and a photocatalyst (porphyrin).[cat] La fotocatàlisi amb llum visible és actualment una de les àrees de recerca més actives en química orgànica, a causa de les possibilitats que ofereix per a la formació d’enllaços C-C i C-Het d’una forma no tòxica i eficient. Si bé la fotocatàlisi amb llum visible ha estat objecte d’un gran interès en els darrers anys, el desenvolupament de processos catalítics enantioselectius promoguts per la llum continua sent extremadament difícil. Per això, un gran nombre de grups de recerca han dedicat els seus esforços en intentar que la fotocatàlisi s’integri amb la catàlisi asimètrica. En aquest context, les transformacions fotocatalítiques asimètriques s’han assolit amb èxit emprant dues metodologies diferents; l’anomenada catàlisi dual, en la que un fotocatalizador es combina amb un co-catalitzador quiral treballant en tàndem per a una única reacció química, i l’anomenada catàlisi bifuncional, en la que un únic catalitzador realitza les funcions de foto- i d’organo- catalitzador, essent aquesta darrera la metodologia menys explorada atesa la dificultat de dissenyar i sintetitzar un catalitzador bifuncional adient. En els darrers anys, les porfirines, com la meso-tetrafenilporfirina (TPP), han estat postulades com a fotocatalitzadors orgànics adients pel desenvolupament de noves metodologies per a la construcció de nous enllaços C-C i C-Het, evitant la utilització de fotocatalitzadors basats en metalls de transició. En aquest camp de recerca, alguns treballs recents mostren la capacitat de les porfirines per actuar com a catalitzadors fotoredox en la reacció organofotocatalítica racèmica d’alfa-alquilació d’aldehids amb diazoacetats, romanent inexplorada la seva versió asimètrica. A causa de l’interès del nostre grup de recerca per les noves aplicacions catalítiques de les porfirines, vam ser especialment atrets per aquests treballs. La present Tesi Doctoral es centre en l’estudi de la cicloaddició asimètrica de Diels-Alder tant en condicions tèrmiques com fotoquímiques i en el desenvolupament d’una versió enantioselectiva per a l’ alfa-alquilació d’aldehids amb diazoacetats. A més, es presenten diversos fotoaminocatalitzadors bifuncionals basats en porfirines mitjançant la combinació d’un organocatalizador (amines secundàries quirals) amb un fotocatalitzador (porfirina).Universitat de BarcelonaMoyano i Baldoire, AlbertUniversitat de Barcelona. Departament de Química Inorgànica i Orgànica2022info:eu-repo/semantics/doctoralThesisinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://hdl.handle.net/2445/192125http://hdl.handle.net/10803/687402Tesis Doctorals - Departament - Química Inorgànica i Orgànicareponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglés(c) Torres Yeste, Pol, 2023info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/1921252026-05-27T06:46:51Z |
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15.300719 |