Synthesis of N-heterocycles and building blocks using multicomponent, photochemical and electrochemical approaches
Autor(a) principal: | |
---|---|
Data de Publicação: | 2020 |
Tipo de documento: | Tese |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/13006 |
Resumo: | Multicomponent reactions and protocols mediated by light and electrochemistry are powerful tools for modern organic synthesis. Moreover, they obey several principles of green chemistry such as atom economy, catalysis, waste reduction, energy efficiency, mild reaction conditions, etc. Therefore, the development of new synthetic methodologies employing these powerful tools is highly desirable and challenging. Chapter 1 describes the efficiency of NbCl5 for the promotion of MCRs between 4-formylphthalonitrile, anilines, and phenylacetylenes through a pericyclic hetero-Diels-Alder process. This multicomponent approach exhibited a wide substrate scope and, to demonstrate the versatility of the phthalonitrile library, we synthesized and characterized three new phthalocyanine derivatives. Chapter 2 covers a metal-free methodology for the photoarylation of pyridines and other heterocycles (such as quinoline and quinoxaline) with aryldiazonium salts in water using a homemade photoreactor. This photochemical approach displayed a broad scope regarding the diazonium salt component and further mechanistic investigations support a mechanism through an EDA complex. Finally, chapter 3 outlines the synthesis of sulfonyl fluorides through electrochemical oxidative coupling of thiols and potassium fluoride. This approach also showed a wide substrate scope, including a variety of alkyl, benzyl, aryl, and heteroaryl thiols or disulfides. Furthermore, kinetic and other additional studies were performed in an attempt to clarify the mechanism of this electrochemical reaction. |
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Bartolomeu, Aloisio de AndradeOliveira, Kleber Thiago dehttp://lattes.cnpq.br/3759761373942891http://lattes.cnpq.br/1673141193455660a1fb54cf-a875-476a-8c6f-304811e29a0d2020-07-04T13:44:45Z2020-07-04T13:44:45Z2020-02-17BARTOLOMEU, Aloisio de Andrade. Synthesis of N-heterocycles and building blocks using multicomponent, photochemical and electrochemical approaches. 2020. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2020. Disponível em: https://repositorio.ufscar.br/handle/ufscar/13006.https://repositorio.ufscar.br/handle/ufscar/13006Multicomponent reactions and protocols mediated by light and electrochemistry are powerful tools for modern organic synthesis. Moreover, they obey several principles of green chemistry such as atom economy, catalysis, waste reduction, energy efficiency, mild reaction conditions, etc. Therefore, the development of new synthetic methodologies employing these powerful tools is highly desirable and challenging. Chapter 1 describes the efficiency of NbCl5 for the promotion of MCRs between 4-formylphthalonitrile, anilines, and phenylacetylenes through a pericyclic hetero-Diels-Alder process. This multicomponent approach exhibited a wide substrate scope and, to demonstrate the versatility of the phthalonitrile library, we synthesized and characterized three new phthalocyanine derivatives. Chapter 2 covers a metal-free methodology for the photoarylation of pyridines and other heterocycles (such as quinoline and quinoxaline) with aryldiazonium salts in water using a homemade photoreactor. This photochemical approach displayed a broad scope regarding the diazonium salt component and further mechanistic investigations support a mechanism through an EDA complex. Finally, chapter 3 outlines the synthesis of sulfonyl fluorides through electrochemical oxidative coupling of thiols and potassium fluoride. This approach also showed a wide substrate scope, including a variety of alkyl, benzyl, aryl, and heteroaryl thiols or disulfides. Furthermore, kinetic and other additional studies were performed in an attempt to clarify the mechanism of this electrochemical reaction.Reações multicomponentes e protocolos mediados por luz e eletroquímica são ferramentas poderosas para a síntese orgânica moderna. Além disso, elas obedecem a vários princípios da química verde, tais como: economia atômica, catálise, redução de resíduos, eficiência energética, condições brandas de reação, etc. Portanto, o desenvolvimento de novas metodologias sintéticas, empregando essas ferramentas poderosas, é altamente desejável e desafiador. O capítulo 1 descreve a eficiência do NbCl5 para a promoção de RMCs entre 4-formilftalonitrilo, anilinas e fenilacetilenos através de um processo pericíclico de hetero-Diels-Alder. Essa abordagem multicomponente exibiu um amplo escopo de substrato e, para demonstrar a versatilidade da biblioteca de ftalonitrilos, três novos derivados ftalocianínicos foram sintetizados e caracterizados. O capítulo 2 aborda uma metodologia livre de metais para a fotoarilação de piridinas e outros heterociclos (tais como quinolina e quinoxalina) com sais de arenodiazônio, em água, usando um fotorreator construído de forma artesanal. Essa abordagem fotoquímica demonstrou um amplo escopo de substrato em relação ao componente sal de diazônio e investigações adicionais do mecanismo reacional suportam um mecanismo através de um complexo EDA. Finalmente, o capítulo 3 apresenta a síntese de fluoretos de sulfonila através do acoplamento oxidativo eletroquímico de tióis e fluoreto de potássio. Essa abordagem também mostrou um amplo escopo de substrato, incluindo uma variedade de alquil, benzil, aril e heteroaril tióis ou dissulfetos. Além disso, estudos cinéticos e outros estudos adicionais foram realizados na tentativa de esclarecer o mecanismo dessa reação eletroquímica.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)CAPES: Código de Financiamento 001FAPESP: 14/24506-3FAPESP: 18/08772-6engUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarAttribution-NonCommercial-NoDerivs 3.0 Brazilhttp://creativecommons.org/licenses/by-nc-nd/3.0/br/info:eu-repo/semantics/openAccessReações multicomponentesFtalonitriloFotocatáliseEletrossínteseSal de arenodiazônioComplexo EDAFluoreto de sulfonilaMulticomponent reactionsPhthalonitrilePhotocatalysisElectrosynthesisAryldiazonium saltEDA complexSulfonyl fluorideCIENCIAS EXATAS E DA TERRA::QUIMICACIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA::SINTESE ORGANICASynthesis of N-heterocycles and building blocks using multicomponent, photochemical and electrochemical approachesSíntese de N-heterociclos e blocos de construção usando abordagens multicomponente, fotoquímica e eletroquímicainfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesis600600ae02a3fa-cd1d-4c64-9580-4ad2f3715a6freponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALAAB_2020.pdfAAB_2020.pdfapplication/pdf22143793https://repositorio.ufscar.br/bitstream/ufscar/13006/1/AAB_2020.pdf89846cbd0e6d768c5c891b6946b6f98aMD51Carta comprovante da versão final da tese.pdfCarta comprovante da versão final da tese.pdfapplication/pdf158966https://repositorio.ufscar.br/bitstream/ufscar/13006/2/Carta%20comprovante%20da%20vers%c3%a3o%20final%20da%20tese.pdfdaa8581189f71a336e7b93790a5ecb8aMD52CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8811https://repositorio.ufscar.br/bitstream/ufscar/13006/3/license_rdfe39d27027a6cc9cb039ad269a5db8e34MD53TEXTAAB_2020.pdf.txtAAB_2020.pdf.txtExtracted texttext/plain0https://repositorio.ufscar.br/bitstream/ufscar/13006/4/AAB_2020.pdf.txtd41d8cd98f00b204e9800998ecf8427eMD54Carta comprovante da versão final da tese.pdf.txtCarta comprovante da versão final da tese.pdf.txtExtracted texttext/plain1446https://repositorio.ufscar.br/bitstream/ufscar/13006/6/Carta%20comprovante%20da%20vers%c3%a3o%20final%20da%20tese.pdf.txt4ae3e7cdfedf9b9fb71f52804369aa21MD56THUMBNAILAAB_2020.pdf.jpgAAB_2020.pdf.jpgIM Thumbnailimage/jpeg10644https://repositorio.ufscar.br/bitstream/ufscar/13006/5/AAB_2020.pdf.jpgf899742eef2b53cd57a6d56ae3fda2baMD55Carta comprovante da versão final da tese.pdf.jpgCarta comprovante da versão final da tese.pdf.jpgIM Thumbnailimage/jpeg10861https://repositorio.ufscar.br/bitstream/ufscar/13006/7/Carta%20comprovante%20da%20vers%c3%a3o%20final%20da%20tese.pdf.jpg4eb02a8a0637042e32f19a184acc91a5MD57ufscar/130062023-09-18 18:31:56.943oai:repositorio.ufscar.br:ufscar/13006Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:31:56Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.eng.fl_str_mv |
Synthesis of N-heterocycles and building blocks using multicomponent, photochemical and electrochemical approaches |
dc.title.alternative.por.fl_str_mv |
Síntese de N-heterociclos e blocos de construção usando abordagens multicomponente, fotoquímica e eletroquímica |
title |
Synthesis of N-heterocycles and building blocks using multicomponent, photochemical and electrochemical approaches |
spellingShingle |
Synthesis of N-heterocycles and building blocks using multicomponent, photochemical and electrochemical approaches Bartolomeu, Aloisio de Andrade Reações multicomponentes Ftalonitrilo Fotocatálise Eletrossíntese Sal de arenodiazônio Complexo EDA Fluoreto de sulfonila Multicomponent reactions Phthalonitrile Photocatalysis Electrosynthesis Aryldiazonium salt EDA complex Sulfonyl fluoride CIENCIAS EXATAS E DA TERRA::QUIMICA CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA::SINTESE ORGANICA |
title_short |
Synthesis of N-heterocycles and building blocks using multicomponent, photochemical and electrochemical approaches |
title_full |
Synthesis of N-heterocycles and building blocks using multicomponent, photochemical and electrochemical approaches |
title_fullStr |
Synthesis of N-heterocycles and building blocks using multicomponent, photochemical and electrochemical approaches |
title_full_unstemmed |
Synthesis of N-heterocycles and building blocks using multicomponent, photochemical and electrochemical approaches |
title_sort |
Synthesis of N-heterocycles and building blocks using multicomponent, photochemical and electrochemical approaches |
author |
Bartolomeu, Aloisio de Andrade |
author_facet |
Bartolomeu, Aloisio de Andrade |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/1673141193455660 |
dc.contributor.author.fl_str_mv |
Bartolomeu, Aloisio de Andrade |
dc.contributor.advisor1.fl_str_mv |
Oliveira, Kleber Thiago de |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/3759761373942891 |
dc.contributor.authorID.fl_str_mv |
a1fb54cf-a875-476a-8c6f-304811e29a0d |
contributor_str_mv |
Oliveira, Kleber Thiago de |
dc.subject.por.fl_str_mv |
Reações multicomponentes Ftalonitrilo Fotocatálise Eletrossíntese Sal de arenodiazônio Complexo EDA Fluoreto de sulfonila |
topic |
Reações multicomponentes Ftalonitrilo Fotocatálise Eletrossíntese Sal de arenodiazônio Complexo EDA Fluoreto de sulfonila Multicomponent reactions Phthalonitrile Photocatalysis Electrosynthesis Aryldiazonium salt EDA complex Sulfonyl fluoride CIENCIAS EXATAS E DA TERRA::QUIMICA CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA::SINTESE ORGANICA |
dc.subject.eng.fl_str_mv |
Multicomponent reactions Phthalonitrile Photocatalysis Electrosynthesis Aryldiazonium salt EDA complex Sulfonyl fluoride |
dc.subject.cnpq.fl_str_mv |
CIENCIAS EXATAS E DA TERRA::QUIMICA CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA::SINTESE ORGANICA |
description |
Multicomponent reactions and protocols mediated by light and electrochemistry are powerful tools for modern organic synthesis. Moreover, they obey several principles of green chemistry such as atom economy, catalysis, waste reduction, energy efficiency, mild reaction conditions, etc. Therefore, the development of new synthetic methodologies employing these powerful tools is highly desirable and challenging. Chapter 1 describes the efficiency of NbCl5 for the promotion of MCRs between 4-formylphthalonitrile, anilines, and phenylacetylenes through a pericyclic hetero-Diels-Alder process. This multicomponent approach exhibited a wide substrate scope and, to demonstrate the versatility of the phthalonitrile library, we synthesized and characterized three new phthalocyanine derivatives. Chapter 2 covers a metal-free methodology for the photoarylation of pyridines and other heterocycles (such as quinoline and quinoxaline) with aryldiazonium salts in water using a homemade photoreactor. This photochemical approach displayed a broad scope regarding the diazonium salt component and further mechanistic investigations support a mechanism through an EDA complex. Finally, chapter 3 outlines the synthesis of sulfonyl fluorides through electrochemical oxidative coupling of thiols and potassium fluoride. This approach also showed a wide substrate scope, including a variety of alkyl, benzyl, aryl, and heteroaryl thiols or disulfides. Furthermore, kinetic and other additional studies were performed in an attempt to clarify the mechanism of this electrochemical reaction. |
publishDate |
2020 |
dc.date.accessioned.fl_str_mv |
2020-07-04T13:44:45Z |
dc.date.available.fl_str_mv |
2020-07-04T13:44:45Z |
dc.date.issued.fl_str_mv |
2020-02-17 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
BARTOLOMEU, Aloisio de Andrade. Synthesis of N-heterocycles and building blocks using multicomponent, photochemical and electrochemical approaches. 2020. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2020. Disponível em: https://repositorio.ufscar.br/handle/ufscar/13006. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/13006 |
identifier_str_mv |
BARTOLOMEU, Aloisio de Andrade. Synthesis of N-heterocycles and building blocks using multicomponent, photochemical and electrochemical approaches. 2020. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2020. Disponível em: https://repositorio.ufscar.br/handle/ufscar/13006. |
url |
https://repositorio.ufscar.br/handle/ufscar/13006 |
dc.language.iso.fl_str_mv |
eng |
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eng |
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600 600 |
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ae02a3fa-cd1d-4c64-9580-4ad2f3715a6f |
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Attribution-NonCommercial-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nc-nd/3.0/br/ info:eu-repo/semantics/openAccess |
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Attribution-NonCommercial-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nc-nd/3.0/br/ |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Universidade Federal de São Carlos Câmpus São Carlos |
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Programa de Pós-Graduação em Química - PPGQ |
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UFSCar |
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Universidade Federal de São Carlos Câmpus São Carlos |
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Universidade Federal de São Carlos (UFSCAR) |
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UFSCAR |
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UFSCAR |
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Repositório Institucional da UFSCAR |
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