Novas abordagens na síntese de heterociclos com potencial aplicação na síntese de moléculas bioativas
Autor(a) principal: | |
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Data de Publicação: | 2017 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/10521 |
Resumo: | Cobalt-catalyzed oxidative cyclization of gem-disubstituted conjugated alkenols: In this part of the work we applied the Mukaiyama Oxidative Ciclization under oxidative and reduced termination conditions aiming the preparation of trisubstituted 2,5,5-THFs-trans from gemdisubstituted aromatic conjugated olefins with different electronic properties. The THFs were obtained only under reduced termination conditions, with of 32-44% of yields. Under oxidative termination conditions, only products from secondary radical reactions that competed with the oxidative cyclization reaction were observed. In addition, the diastereoselectivity involved in this process was evaluated,, which in this case were obtained in 17-46% of yields and dr 2.5:1 to 5.4: 1. Preparation of 1H-1,2,3-triazole under more sustainable conditions: In this second part of the work the main objective was to develop an one-pot methodology for the preparation of 1H-1,2,3-triazoles from nitrolefins. This methodology is inserted in a concept of a more sustainable chemistry, since the obtaining heterocyclics was carried out through a metal-free approach, using the green solvent PEG400, and the direct use of sodium azide. The 1H-1,2,3-triazoles were obtained via one-pot reaction in good yields (54-80%). |
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Alves, Tânia Mara FerreiraFerreira, Marco Antonio Barbosahttp://lattes.cnpq.br/6874055640224407http://lattes.cnpq.br/2711137157839870d0688af2-bd5b-4594-89c0-44e4fd53d49a2018-09-28T00:07:44Z2018-09-28T00:07:44Z2017-08-04ALVES, Tânia Mara Ferreira. Novas abordagens na síntese de heterociclos com potencial aplicação na síntese de moléculas bioativas. 2017. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2017. Disponível em: https://repositorio.ufscar.br/handle/ufscar/10521.https://repositorio.ufscar.br/handle/ufscar/10521Cobalt-catalyzed oxidative cyclization of gem-disubstituted conjugated alkenols: In this part of the work we applied the Mukaiyama Oxidative Ciclization under oxidative and reduced termination conditions aiming the preparation of trisubstituted 2,5,5-THFs-trans from gemdisubstituted aromatic conjugated olefins with different electronic properties. The THFs were obtained only under reduced termination conditions, with of 32-44% of yields. Under oxidative termination conditions, only products from secondary radical reactions that competed with the oxidative cyclization reaction were observed. In addition, the diastereoselectivity involved in this process was evaluated,, which in this case were obtained in 17-46% of yields and dr 2.5:1 to 5.4: 1. Preparation of 1H-1,2,3-triazole under more sustainable conditions: In this second part of the work the main objective was to develop an one-pot methodology for the preparation of 1H-1,2,3-triazoles from nitrolefins. This methodology is inserted in a concept of a more sustainable chemistry, since the obtaining heterocyclics was carried out through a metal-free approach, using the green solvent PEG400, and the direct use of sodium azide. The 1H-1,2,3-triazoles were obtained via one-pot reaction in good yields (54-80%).Novas abordagens na síntese de heterociclos com potencial aplicação na síntese de moléculas bioativas Ciclização Oxidativa catalisada por cobalto de alquenóis conjugados gem-dissubstituídos: Nesta primeira etapa do trabalho empregamos a Ciclização Oxidativa de Mukaiyama em condições de terminação oxidativa e redutiva com o objetivo de preparar 2,5,5-THFs-trans trisubstituídos a partir de olefinas gem-dissubstituídas conjugadas a grupos aromáticos com diferentes propriedades eletrônicas. A unidade de interesse foi obtida apenas em condições de terminação redutiva, com rendimentos de 32-44%. Em condições de terminação oxidativa obteve-se apenas produtos provenientes de reações radicalares secundárias que competiam com a reação de ciclização oxidativa. Em uma etapa mais avançada deste trabalho avaliou-se a diastereosseletividade envolvida neste processo, os quais neste estudo foram obtidos com rendimentos de 17-46% e dr 2,5:1 para 5,4:1. Preparação de 1H-1,2,3-triazol em condições mais sustentáveis: Nesta segunda parte do trabalho o objetivo foi desenvolver uma metodologia “one-pot” para a preparação de diferentes 1H-1,2,3-triazóis a partir de nitrolefinas. Esta metodologia encontra-se inserida em um conceito de uma química mais sustentável, visto que, a obtenção destes heterocíclicos foi realizada através de reações “metal-free”, na qual foi empregado o solvente verde PEG400 e foi feito o uso direto de azida de sódio. Os 1H-1,2,3-triazóis foram obtidos via reação “one-pot” em bons rendimentos (54-80%).Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)porUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarHeterociclosMoléculas bioativasHeterocyclesBioactive moleculesCIENCIAS EXATAS E DA TERRA::QUIMICANovas abordagens na síntese de heterociclos com potencial aplicação na síntese de moléculas bioativasNew approaches in the synthesis of heterocycles with potencial application in the synthesis of bioactive moleculesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisOnline60060031144104-e78d-4438-831f-39dae3ba73cdinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALTese-Tania-PPGQ-UFSCar.pdfTese-Tania-PPGQ-UFSCar.pdfapplication/pdf7528301https://repositorio.ufscar.br/bitstream/ufscar/10521/1/Tese-Tania-PPGQ-UFSCar.pdf15b8484d1cf717dad03a1eeaf2d24554MD51LICENSElicense.txtlicense.txttext/plain; charset=utf-81957https://repositorio.ufscar.br/bitstream/ufscar/10521/4/license.txtae0398b6f8b235e40ad82cba6c50031dMD54TEXTTese-Tania-PPGQ-UFSCar.pdf.txtTese-Tania-PPGQ-UFSCar.pdf.txtExtracted texttext/plain273698https://repositorio.ufscar.br/bitstream/ufscar/10521/5/Tese-Tania-PPGQ-UFSCar.pdf.txt24b920a7d8c4d660a9dc143c45ebad21MD55THUMBNAILTese-Tania-PPGQ-UFSCar.pdf.jpgTese-Tania-PPGQ-UFSCar.pdf.jpgIM Thumbnailimage/jpeg9538https://repositorio.ufscar.br/bitstream/ufscar/10521/6/Tese-Tania-PPGQ-UFSCar.pdf.jpg1f74b40426f2eda519f1951907d931d6MD56ufscar/105212023-09-18 18:31:17.093oai:repositorio.ufscar.br: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Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:31:17Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.por.fl_str_mv |
Novas abordagens na síntese de heterociclos com potencial aplicação na síntese de moléculas bioativas |
dc.title.alternative.eng.fl_str_mv |
New approaches in the synthesis of heterocycles with potencial application in the synthesis of bioactive molecules |
title |
Novas abordagens na síntese de heterociclos com potencial aplicação na síntese de moléculas bioativas |
spellingShingle |
Novas abordagens na síntese de heterociclos com potencial aplicação na síntese de moléculas bioativas Alves, Tânia Mara Ferreira Heterociclos Moléculas bioativas Heterocycles Bioactive molecules CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Novas abordagens na síntese de heterociclos com potencial aplicação na síntese de moléculas bioativas |
title_full |
Novas abordagens na síntese de heterociclos com potencial aplicação na síntese de moléculas bioativas |
title_fullStr |
Novas abordagens na síntese de heterociclos com potencial aplicação na síntese de moléculas bioativas |
title_full_unstemmed |
Novas abordagens na síntese de heterociclos com potencial aplicação na síntese de moléculas bioativas |
title_sort |
Novas abordagens na síntese de heterociclos com potencial aplicação na síntese de moléculas bioativas |
author |
Alves, Tânia Mara Ferreira |
author_facet |
Alves, Tânia Mara Ferreira |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/2711137157839870 |
dc.contributor.author.fl_str_mv |
Alves, Tânia Mara Ferreira |
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 |
d0688af2-bd5b-4594-89c0-44e4fd53d49a |
contributor_str_mv |
Ferreira, Marco Antonio Barbosa |
dc.subject.por.fl_str_mv |
Heterociclos Moléculas bioativas |
topic |
Heterociclos Moléculas bioativas Heterocycles Bioactive molecules CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Heterocycles Bioactive molecules |
dc.subject.cnpq.fl_str_mv |
CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
Cobalt-catalyzed oxidative cyclization of gem-disubstituted conjugated alkenols: In this part of the work we applied the Mukaiyama Oxidative Ciclization under oxidative and reduced termination conditions aiming the preparation of trisubstituted 2,5,5-THFs-trans from gemdisubstituted aromatic conjugated olefins with different electronic properties. The THFs were obtained only under reduced termination conditions, with of 32-44% of yields. Under oxidative termination conditions, only products from secondary radical reactions that competed with the oxidative cyclization reaction were observed. In addition, the diastereoselectivity involved in this process was evaluated,, which in this case were obtained in 17-46% of yields and dr 2.5:1 to 5.4: 1. Preparation of 1H-1,2,3-triazole under more sustainable conditions: In this second part of the work the main objective was to develop an one-pot methodology for the preparation of 1H-1,2,3-triazoles from nitrolefins. This methodology is inserted in a concept of a more sustainable chemistry, since the obtaining heterocyclics was carried out through a metal-free approach, using the green solvent PEG400, and the direct use of sodium azide. The 1H-1,2,3-triazoles were obtained via one-pot reaction in good yields (54-80%). |
publishDate |
2017 |
dc.date.issued.fl_str_mv |
2017-08-04 |
dc.date.accessioned.fl_str_mv |
2018-09-28T00:07:44Z |
dc.date.available.fl_str_mv |
2018-09-28T00:07:44Z |
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 |
ALVES, Tânia Mara Ferreira. Novas abordagens na síntese de heterociclos com potencial aplicação na síntese de moléculas bioativas. 2017. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2017. Disponível em: https://repositorio.ufscar.br/handle/ufscar/10521. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/10521 |
identifier_str_mv |
ALVES, Tânia Mara Ferreira. Novas abordagens na síntese de heterociclos com potencial aplicação na síntese de moléculas bioativas. 2017. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2017. Disponível em: https://repositorio.ufscar.br/handle/ufscar/10521. |
url |
https://repositorio.ufscar.br/handle/ufscar/10521 |
dc.language.iso.fl_str_mv |
por |
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por |
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600 600 |
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info:eu-repo/semantics/openAccess |
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openAccess |
dc.publisher.none.fl_str_mv |
Universidade Federal de São Carlos Câmpus São Carlos |
dc.publisher.program.fl_str_mv |
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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