Síntese de furanos trissubstituídos via reações de oxopaladação aeróbica
Autor(a) principal: | |
---|---|
Data de Publicação: | 2019 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/11140 |
Resumo: | Furans are important heterocyclics with broad application in synthesis as a building block, frequently presented in a wide range of compounds that exhibit biological activity, including natural products. Intramolecular oxopallation chemistry has been widely applied for the preparation of furans and benzofurans, with particular emphasis on processes of intramolecular cycloisomerization of substituted carbonyl precursors. However, the use of 2-alkenylcarbonyls, more accessible and easily manipulated than the previous starting materials, is still unexplored with palladium II chemistry. It is well known that the use of oxidants to regenerate the reactive species of palladium is necessary and that an aerobic version of these reactions represents a major advance due to the widespread availability of molecular oxygen as a "green" oxidant. The present work demonstrates the development of an aerobic methodology for the direct use of molecular oxygen in the synthesis of trisubstituted furans using β-ketoesters derivatives and palladium II source. In the initial attempt to synthesize the furans, reactive systems such as alkenyl-substituted β-ketoesters were explored. In sequence, experiments were carried out with the variation of the catalyst source, solvents, additives and temperature, in order to find the optimized condition for the oxopallation reaction. Stands out the use of bis (acetonitrile) dichloro-palladium as catalyst, dimethylformamide and sodium acetate as solvent and base, respectively, and molecular sieve of 4 Å at 40 °C under an atmosphere of 1 atm of molecular oxygen. With the optimized reaction conditions, it was tested for other substrates in order to evaluate the scope of this methodology. The studies to verify the scope of the methodology were carried out providing yields up to 85% for the 21 substrates evaluated. |
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Barboza, Amanda AlineFerreira, Marco Antonio Barbosahttp://lattes.cnpq.br/6874055640224407http://lattes.cnpq.br/4255739684342248d4abcd7d-c440-4791-9d9e-94a478bd0c852019-03-27T14:02:40Z2019-03-27T14:02:40Z2019-02-25BARBOZA, Amanda Aline. Síntese de furanos trissubstituídos via reações de oxopaladação aeróbica. 2019. Dissertação (Mestrado em Química) – Universidade Federal de São Carlos, São Carlos, 2019. Disponível em: https://repositorio.ufscar.br/handle/ufscar/11140.https://repositorio.ufscar.br/handle/ufscar/11140Furans are important heterocyclics with broad application in synthesis as a building block, frequently presented in a wide range of compounds that exhibit biological activity, including natural products. Intramolecular oxopallation chemistry has been widely applied for the preparation of furans and benzofurans, with particular emphasis on processes of intramolecular cycloisomerization of substituted carbonyl precursors. However, the use of 2-alkenylcarbonyls, more accessible and easily manipulated than the previous starting materials, is still unexplored with palladium II chemistry. It is well known that the use of oxidants to regenerate the reactive species of palladium is necessary and that an aerobic version of these reactions represents a major advance due to the widespread availability of molecular oxygen as a "green" oxidant. The present work demonstrates the development of an aerobic methodology for the direct use of molecular oxygen in the synthesis of trisubstituted furans using β-ketoesters derivatives and palladium II source. In the initial attempt to synthesize the furans, reactive systems such as alkenyl-substituted β-ketoesters were explored. In sequence, experiments were carried out with the variation of the catalyst source, solvents, additives and temperature, in order to find the optimized condition for the oxopallation reaction. Stands out the use of bis (acetonitrile) dichloro-palladium as catalyst, dimethylformamide and sodium acetate as solvent and base, respectively, and molecular sieve of 4 Å at 40 °C under an atmosphere of 1 atm of molecular oxygen. With the optimized reaction conditions, it was tested for other substrates in order to evaluate the scope of this methodology. The studies to verify the scope of the methodology were carried out providing yields up to 85% for the 21 substrates evaluated.Furanos são importantes heterocíclicos utilizados em síntese como bloco de construção e frequentemente encontrados como unidades em uma ampla gama de compostos que apresentam atividade biológica, além da grande ocorrência em produtos naturais. A química de oxopaladação intramolecular foi amplamente aplicada para a preparação de furanos e benzofuranos, com especial destaque em processos de cicloisomerização intramolecular de precursores carbonílicos substituídos. Contudo, o uso de 2-alquenilcarbonilas, compostos mais acessíveis e mais facilmente manipuláveis do que os derivados geralmente utilizados, tem sido muito pouco explorada com a química de paládio II. Acrescenta-se que o uso de oxidantes para regenerar as espécies reativas de paládio se faz necessário e que uma versão aeróbica dessas reações representa um grande avanço visto a ampla disponibilidade do oxigênio molecular como oxidante “verde”. O presente trabalho demonstra o desenvolvimento de uma metodologia aeróbica com utilização direta de oxigênio molecular na síntese de furanos trissubstituídos através de nucleopaladação aeróbica, utilizando derivados β-cetoesteres e fonte de paládio II. Na tentativa inicial de sintetizar os furanos, explorou-se sistemas reativos como os β-cetoésteres substituído com alquenil. Em sequência, experimentos foram realizados com a variação da fonte de catalisador, solventes, aditivos e temperatura, afim de encontrar-se a condição otimizada para a reação de oxopaladação. Destacando-se a que fez uso de bis(acetonitrila)dicloro paládio como catalisador, dimetilformamida e acetato de sódio como solvente e base, respectivamente, e peneira molecular de 4 Å a temperatura de 40 ºC sob atmosfera de 1 atm de oxigênio molecular. Com as condições reacionais otimizadas, esta foi testada para outros substratos afim de avaliar-se a abrangência dessa metodologia. Os estudos para averiguar a abrangência da metodologia foram realizados fornecendo rendimentos de até 85% para os 21 substratos avaliados.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)porUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarFuranosOxopaladaçãoAeróbicaCIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA::SINTESE ORGANICASíntese de furanos trissubstituídos via reações de oxopaladação aeróbicainfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisOnline60060031144104-e78d-4438-831f-39dae3ba73cdinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALDissertacao-versao final.pdfDissertacao-versao final.pdfDissertação de mestradoapplication/pdf20042042https://repositorio.ufscar.br/bitstream/ufscar/11140/1/Dissertacao-versao%20final.pdf487e9f08bb316b4537a1668c6fa4caecMD51LICENSElicense.txtlicense.txttext/plain; charset=utf-81957https://repositorio.ufscar.br/bitstream/ufscar/11140/4/license.txtae0398b6f8b235e40ad82cba6c50031dMD54TEXTDissertacao-versao final.pdf.txtDissertacao-versao final.pdf.txtExtracted texttext/plain191193https://repositorio.ufscar.br/bitstream/ufscar/11140/5/Dissertacao-versao%20final.pdf.txtf5bfb42c36f9c023b3e091ae727f1ff0MD55THUMBNAILDissertacao-versao final.pdf.jpgDissertacao-versao final.pdf.jpgIM Thumbnailimage/jpeg8878https://repositorio.ufscar.br/bitstream/ufscar/11140/6/Dissertacao-versao%20final.pdf.jpg317b705c9da33428301041cff3c51de1MD56ufscar/111402023-09-18 18:31:21.079oai:repositorio.ufscar.br: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Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:31:21Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.por.fl_str_mv |
Síntese de furanos trissubstituídos via reações de oxopaladação aeróbica |
title |
Síntese de furanos trissubstituídos via reações de oxopaladação aeróbica |
spellingShingle |
Síntese de furanos trissubstituídos via reações de oxopaladação aeróbica Barboza, Amanda Aline Furanos Oxopaladação Aeróbica CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA::SINTESE ORGANICA |
title_short |
Síntese de furanos trissubstituídos via reações de oxopaladação aeróbica |
title_full |
Síntese de furanos trissubstituídos via reações de oxopaladação aeróbica |
title_fullStr |
Síntese de furanos trissubstituídos via reações de oxopaladação aeróbica |
title_full_unstemmed |
Síntese de furanos trissubstituídos via reações de oxopaladação aeróbica |
title_sort |
Síntese de furanos trissubstituídos via reações de oxopaladação aeróbica |
author |
Barboza, Amanda Aline |
author_facet |
Barboza, Amanda Aline |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/4255739684342248 |
dc.contributor.author.fl_str_mv |
Barboza, Amanda Aline |
dc.contributor.advisor1.fl_str_mv |
Ferreira, Marco Antonio Barbosa |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/6874055640224407 |
dc.contributor.authorID.fl_str_mv |
d4abcd7d-c440-4791-9d9e-94a478bd0c85 |
contributor_str_mv |
Ferreira, Marco Antonio Barbosa |
dc.subject.por.fl_str_mv |
Furanos Oxopaladação Aeróbica |
topic |
Furanos Oxopaladação Aeróbica CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA::SINTESE ORGANICA |
dc.subject.cnpq.fl_str_mv |
CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA::SINTESE ORGANICA |
description |
Furans are important heterocyclics with broad application in synthesis as a building block, frequently presented in a wide range of compounds that exhibit biological activity, including natural products. Intramolecular oxopallation chemistry has been widely applied for the preparation of furans and benzofurans, with particular emphasis on processes of intramolecular cycloisomerization of substituted carbonyl precursors. However, the use of 2-alkenylcarbonyls, more accessible and easily manipulated than the previous starting materials, is still unexplored with palladium II chemistry. It is well known that the use of oxidants to regenerate the reactive species of palladium is necessary and that an aerobic version of these reactions represents a major advance due to the widespread availability of molecular oxygen as a "green" oxidant. The present work demonstrates the development of an aerobic methodology for the direct use of molecular oxygen in the synthesis of trisubstituted furans using β-ketoesters derivatives and palladium II source. In the initial attempt to synthesize the furans, reactive systems such as alkenyl-substituted β-ketoesters were explored. In sequence, experiments were carried out with the variation of the catalyst source, solvents, additives and temperature, in order to find the optimized condition for the oxopallation reaction. Stands out the use of bis (acetonitrile) dichloro-palladium as catalyst, dimethylformamide and sodium acetate as solvent and base, respectively, and molecular sieve of 4 Å at 40 °C under an atmosphere of 1 atm of molecular oxygen. With the optimized reaction conditions, it was tested for other substrates in order to evaluate the scope of this methodology. The studies to verify the scope of the methodology were carried out providing yields up to 85% for the 21 substrates evaluated. |
publishDate |
2019 |
dc.date.accessioned.fl_str_mv |
2019-03-27T14:02:40Z |
dc.date.available.fl_str_mv |
2019-03-27T14:02:40Z |
dc.date.issued.fl_str_mv |
2019-02-25 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
format |
masterThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
BARBOZA, Amanda Aline. Síntese de furanos trissubstituídos via reações de oxopaladação aeróbica. 2019. Dissertação (Mestrado em Química) – Universidade Federal de São Carlos, São Carlos, 2019. Disponível em: https://repositorio.ufscar.br/handle/ufscar/11140. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/11140 |
identifier_str_mv |
BARBOZA, Amanda Aline. Síntese de furanos trissubstituídos via reações de oxopaladação aeróbica. 2019. Dissertação (Mestrado em Química) – Universidade Federal de São Carlos, São Carlos, 2019. Disponível em: https://repositorio.ufscar.br/handle/ufscar/11140. |
url |
https://repositorio.ufscar.br/handle/ufscar/11140 |
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por |
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600 600 |
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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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