Síntese e funcionalização de azóis via formação de ligações carbono – carbono e carbono – nitrogênio
Ano de defesa: | 2017 |
---|---|
Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , , , |
Tipo de documento: | Tese |
Tipo de acesso: | Acesso aberto |
Idioma: | por |
Instituição de defesa: |
Universidade Federal de Santa Maria
Centro de Ciências Naturais e Exatas |
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química
|
Departamento: |
Química
|
País: |
Brasil
|
Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/12456 |
Resumo: | This work describes the synthesis and functionalization of azoles employing different methodologies, based on organometallic catalysis or not. Firstly, we disclose the synthesis tetra-substituted 5-trifluoromethyl pyrazoles via sequential halogenation of 5-trifluoromethyl pyrazoles and palladium-catalyzed carbon–carbon and carbon–nitrogen cross-coupling reactions employing organozinc reagents and amines as coupling partners, respectively. This work allowed to achieve new pyrazolic systems in moderated to good yields. Posteriorly, we show the synthesis of 1,3-di(hetero)aryl indazoles exploring the complementary catalytic activity of nickel and copper complexes. We commenced this study evaluating different nickel pre-catalysts to perform the intramolecular amination of unprotected 2-chlorophenyl hydrazones. In a second moment, we described the N-(hetero)arylation of the in situ generated NH indazoles, using a simple catalytic system based on copper/DMEDA. This sequential one-pot fashion procedure allowed the achievement of several 1,3-di(hetero)aryl indazoles in moderate to good yields. Lastly, we disclose the formation of pyrazolo[1,5-a]quinoxalin-4(5H)-ones by the reaction between ethyl 1-(2-chlorophenyl)-1H-pyrazole-5-carboxylate and primary amines. The one-pot methodology undergoes by two sequential reactional pathways: i) amidation of the ester moiety attached to the pyrazole ring, and ii) intramolecular cyclization via nucleophilic aromatic substitution. This synthetic approach proved to be efficient only for primary aliphatic amines, allowing to achieve molecules with different substitution patterns in moderate to good yields. Key-words: Azoles, quinoxalinones, Negishi cross-coupling, Buchwald-Hartwig cross-coupling. |
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2018-02-16T13:41:50Z2018-02-16T13:41:50Z2017-02-24http://repositorio.ufsm.br/handle/1/12456This work describes the synthesis and functionalization of azoles employing different methodologies, based on organometallic catalysis or not. Firstly, we disclose the synthesis tetra-substituted 5-trifluoromethyl pyrazoles via sequential halogenation of 5-trifluoromethyl pyrazoles and palladium-catalyzed carbon–carbon and carbon–nitrogen cross-coupling reactions employing organozinc reagents and amines as coupling partners, respectively. This work allowed to achieve new pyrazolic systems in moderated to good yields. Posteriorly, we show the synthesis of 1,3-di(hetero)aryl indazoles exploring the complementary catalytic activity of nickel and copper complexes. We commenced this study evaluating different nickel pre-catalysts to perform the intramolecular amination of unprotected 2-chlorophenyl hydrazones. In a second moment, we described the N-(hetero)arylation of the in situ generated NH indazoles, using a simple catalytic system based on copper/DMEDA. This sequential one-pot fashion procedure allowed the achievement of several 1,3-di(hetero)aryl indazoles in moderate to good yields. Lastly, we disclose the formation of pyrazolo[1,5-a]quinoxalin-4(5H)-ones by the reaction between ethyl 1-(2-chlorophenyl)-1H-pyrazole-5-carboxylate and primary amines. The one-pot methodology undergoes by two sequential reactional pathways: i) amidation of the ester moiety attached to the pyrazole ring, and ii) intramolecular cyclization via nucleophilic aromatic substitution. This synthetic approach proved to be efficient only for primary aliphatic amines, allowing to achieve molecules with different substitution patterns in moderate to good yields. Key-words: Azoles, quinoxalinones, Negishi cross-coupling, Buchwald-Hartwig cross-coupling.Este trabalho descreve a síntese e a funcionalização de azóis através de diferentes metodologias, ancoradas ou não na catálise organometálica. Primeiramente, descrevemos a síntese de 5-trifluormetil pirazóis tetrassubtituídos através de reações de acoplamento cruzado catalisadas por complexos de paládio entre 5-trifluormetil-4-halo pirazóis, reagentes organozinco e aminas. Este trabalho permitiu a obtenção de novos sistemas pirazólicos com rendimentos moderados a bons. Posteriormente realizamos a síntese de 1,3-di(hetero)aril indazóis explorando as atividades catalíticas complementares de complexos de níquel e cobre. Primeiramente avaliamos diferentes pré-catalisadores de níquel para realizar a aminação intramolecular de diferentes 2-clorofenil hidrazonas não protegidas. Em um segundo momento, realizamos a N-(hetero)arilação dos NH indazóis gerados in situ, através do emprego de um sistema catalítico baseado em cobre/DMEDA. A metodologia permitiu a obtenção de diferentes indazóis 1,3-di(hetero)aril substituídos, com rendimentos moderados a bons. Por fim, demonstramos a síntese de pirazolo[1,5-a]quinoxalin-4(5H)-onas a partir da reação entre 1-(2-clorofenil)-1H-pirazolo-5-carboxilatos de etila e aminas primárias. A metodologia one-pot envolve duas etapas sequenciais; i) amidação da função éster do pirazol e ii) ciclização intramolecular via substituição nucleofílica aromática. Esta abordagem sintética provou ser eficiente ao se empregar aminas alquílicas primárias, permitindo a obtenção de diferentes padrões de substituição com rendimentos moderados a bons.porUniversidade Federal de Santa MariaCentro de Ciências Naturais e ExatasPrograma de Pós-Graduação em QuímicaUFSMBrasilQuímicaAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessAzóisQuinoxalinonasNegishi “cross-coupling”Buchwald-Hartwig “cross-coupling”AzolesQuinoxalinonesCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICASíntese e funcionalização de azóis via formação de ligações carbono – carbono e carbono – nitrogênioSynthesis and functionalization of azoles via carbon-carbon and carbon-nitrogen bonds formationinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisBonacorso, Helio Gauzehttp://lattes.cnpq.br/7275608974248322Galetto, Fabio Zazykihttp://lattes.cnpq.br/1317649922712444Mendes, Samuel Rodrigueshttp://lattes.cnpq.br/6773304655570859Iglesias, Bernardo Almeidahttp://lattes.cnpq.br/4402375533322977Silveira, Claudio da Cruzhttp://lattes.cnpq.br/6152568411858220http://lattes.cnpq.br/5311350037734576Wiethan, Carson Wanderley10060000000060006c852ad-d805-43c3-99d6-93a6a86f507c1775199a-9caa-4da9-8ecc-d713f3b30567b59919f1-10cb-4c65-98b4-9870e812c2d610fc2a99-9f62-43a4-b380-53ccea1ab31e96456df0-a242-4b15-bd73-2f790a5764a8bfcc69ab-e381-4e61-bb0a-13b44161f48dreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALTES_PPGQUIMICA_2017_WIETHAN_CARSON.pdfTES_PPGQUIMICA_2017_WIETHAN_CARSON.pdfTese de Doutoradoapplication/pdf17974788http://repositorio.ufsm.br/bitstream/1/12456/1/TES_PPGQUIMICA_2017_WIETHAN_CARSON.pdf4c3810635ce4a39d77261985e19fe4e2MD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; 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dc.title.por.fl_str_mv |
Síntese e funcionalização de azóis via formação de ligações carbono – carbono e carbono – nitrogênio |
dc.title.alternative.eng.fl_str_mv |
Synthesis and functionalization of azoles via carbon-carbon and carbon-nitrogen bonds formation |
title |
Síntese e funcionalização de azóis via formação de ligações carbono – carbono e carbono – nitrogênio |
spellingShingle |
Síntese e funcionalização de azóis via formação de ligações carbono – carbono e carbono – nitrogênio Wiethan, Carson Wanderley Azóis Quinoxalinonas Negishi “cross-coupling” Buchwald-Hartwig “cross-coupling” Azoles Quinoxalinones CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese e funcionalização de azóis via formação de ligações carbono – carbono e carbono – nitrogênio |
title_full |
Síntese e funcionalização de azóis via formação de ligações carbono – carbono e carbono – nitrogênio |
title_fullStr |
Síntese e funcionalização de azóis via formação de ligações carbono – carbono e carbono – nitrogênio |
title_full_unstemmed |
Síntese e funcionalização de azóis via formação de ligações carbono – carbono e carbono – nitrogênio |
title_sort |
Síntese e funcionalização de azóis via formação de ligações carbono – carbono e carbono – nitrogênio |
author |
Wiethan, Carson Wanderley |
author_facet |
Wiethan, Carson Wanderley |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Bonacorso, Helio Gauze |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/7275608974248322 |
dc.contributor.referee1.fl_str_mv |
Galetto, Fabio Zazyki |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/1317649922712444 |
dc.contributor.referee2.fl_str_mv |
Mendes, Samuel Rodrigues |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/6773304655570859 |
dc.contributor.referee3.fl_str_mv |
Iglesias, Bernardo Almeida |
dc.contributor.referee3Lattes.fl_str_mv |
http://lattes.cnpq.br/4402375533322977 |
dc.contributor.referee4.fl_str_mv |
Silveira, Claudio da Cruz |
dc.contributor.referee4Lattes.fl_str_mv |
http://lattes.cnpq.br/6152568411858220 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/5311350037734576 |
dc.contributor.author.fl_str_mv |
Wiethan, Carson Wanderley |
contributor_str_mv |
Bonacorso, Helio Gauze Galetto, Fabio Zazyki Mendes, Samuel Rodrigues Iglesias, Bernardo Almeida Silveira, Claudio da Cruz |
dc.subject.por.fl_str_mv |
Azóis Quinoxalinonas Negishi “cross-coupling” Buchwald-Hartwig “cross-coupling” |
topic |
Azóis Quinoxalinonas Negishi “cross-coupling” Buchwald-Hartwig “cross-coupling” Azoles Quinoxalinones CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Azoles Quinoxalinones |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This work describes the synthesis and functionalization of azoles employing different methodologies, based on organometallic catalysis or not. Firstly, we disclose the synthesis tetra-substituted 5-trifluoromethyl pyrazoles via sequential halogenation of 5-trifluoromethyl pyrazoles and palladium-catalyzed carbon–carbon and carbon–nitrogen cross-coupling reactions employing organozinc reagents and amines as coupling partners, respectively. This work allowed to achieve new pyrazolic systems in moderated to good yields. Posteriorly, we show the synthesis of 1,3-di(hetero)aryl indazoles exploring the complementary catalytic activity of nickel and copper complexes. We commenced this study evaluating different nickel pre-catalysts to perform the intramolecular amination of unprotected 2-chlorophenyl hydrazones. In a second moment, we described the N-(hetero)arylation of the in situ generated NH indazoles, using a simple catalytic system based on copper/DMEDA. This sequential one-pot fashion procedure allowed the achievement of several 1,3-di(hetero)aryl indazoles in moderate to good yields. Lastly, we disclose the formation of pyrazolo[1,5-a]quinoxalin-4(5H)-ones by the reaction between ethyl 1-(2-chlorophenyl)-1H-pyrazole-5-carboxylate and primary amines. The one-pot methodology undergoes by two sequential reactional pathways: i) amidation of the ester moiety attached to the pyrazole ring, and ii) intramolecular cyclization via nucleophilic aromatic substitution. This synthetic approach proved to be efficient only for primary aliphatic amines, allowing to achieve molecules with different substitution patterns in moderate to good yields. Key-words: Azoles, quinoxalinones, Negishi cross-coupling, Buchwald-Hartwig cross-coupling. |
publishDate |
2017 |
dc.date.issued.fl_str_mv |
2017-02-24 |
dc.date.accessioned.fl_str_mv |
2018-02-16T13:41:50Z |
dc.date.available.fl_str_mv |
2018-02-16T13:41:50Z |
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.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/12456 |
url |
http://repositorio.ufsm.br/handle/1/12456 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.relation.cnpq.fl_str_mv |
100600000000 |
dc.relation.confidence.fl_str_mv |
600 |
dc.relation.authority.fl_str_mv |
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dc.rights.driver.fl_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Química |
dc.publisher.initials.fl_str_mv |
UFSM |
dc.publisher.country.fl_str_mv |
Brasil |
dc.publisher.department.fl_str_mv |
Química |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.source.none.fl_str_mv |
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