Formação de ligações carbono-nitrogênio e carbonocalcogênio catalisadas por iodeto de cobre: síntese de 2- (organocalcogenil)-indolizinas
Ano de defesa: | 2018 |
---|---|
Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , |
Tipo de documento: | Dissertação |
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/1/15602 |
Resumo: | The copper-catalyzed cyclization of propargylpyridines with diorganyl dichalcogenides was applied to the synthesis of 2-(organochalcogenyl)-indolizines. A systematic study of the cyclization system revealed that the mutual action between copper(I) iodide and diorganyl dichalcogenides is essential for the formation of 2- (organochalcogenyl)-indolizines in good yields avoiding the formation of hydrogenated indolizine. The standard reactional conditions with the use of propargylpyridines (0.25 mmol), diorganyl dichalcogenides (0.375 mmol), copper (I) Iodide (20 mol%), sodium carbonate (0.50 mmol) in DMF (3 mL) were compatible with many replacements in the substrate, such as methyl, chlorine, fluoride, methoxyl and trifluoromethyl. This protocol was efficient with diorganyl diselenides and ditellurides but ineffective with diorganyl disulfides. Through this methodology, 27 new molecules were obtained with yields ranging from 21 to 84%. In addition, the 2- (organochalcogenyl)-Indolizines obtained were easily transformed into more complex products using reactions in cross-coupling conditions of the Suzuki type catalyzed by palladium salts with bronic acids. Condition which provided 3 new examples of the 2- aryl-indolizinas with yields of 38 to 73%. |
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2019-02-12T10:51:48Z2019-02-12T10:51:48Z2018-02-28http://repositorio.ufsm.br/handle/1/15602The copper-catalyzed cyclization of propargylpyridines with diorganyl dichalcogenides was applied to the synthesis of 2-(organochalcogenyl)-indolizines. A systematic study of the cyclization system revealed that the mutual action between copper(I) iodide and diorganyl dichalcogenides is essential for the formation of 2- (organochalcogenyl)-indolizines in good yields avoiding the formation of hydrogenated indolizine. The standard reactional conditions with the use of propargylpyridines (0.25 mmol), diorganyl dichalcogenides (0.375 mmol), copper (I) Iodide (20 mol%), sodium carbonate (0.50 mmol) in DMF (3 mL) were compatible with many replacements in the substrate, such as methyl, chlorine, fluoride, methoxyl and trifluoromethyl. This protocol was efficient with diorganyl diselenides and ditellurides but ineffective with diorganyl disulfides. Through this methodology, 27 new molecules were obtained with yields ranging from 21 to 84%. In addition, the 2- (organochalcogenyl)-Indolizines obtained were easily transformed into more complex products using reactions in cross-coupling conditions of the Suzuki type catalyzed by palladium salts with bronic acids. Condition which provided 3 new examples of the 2- aryl-indolizinas with yields of 38 to 73%.A ciclização de piridinas propargílicas catalisada por iodeto de cobre com dicalcogenetos de diorganoíla foi aplicada a síntese de 2-(organocalcogenil)- indolizinas. Um estudo sistemático do sistema de ciclização revelou que a ação mútua entre o iodeto de cobre e dicalcogeneto de diorganoíla é essencial para obtenção das 2-(organocalcogenil)-indolizinas em bons rendimentos, evitando a formação das indolizinas hidrogenadas. As condições reacionais padrões com a utilização da piridina propargílica (0,25 mmol), dicalcogeneto de diorganoíla (0,375 mmol), iodeto de cobre (20 mol%), carbonato de sódio (0,50 mmol) em DMF (3 mL) foram compatveis com muitos substituintes no substrato, tais como metila, cloro, flúor, metoxila e trifluormetila. Este protocolo foi eficiente com diversos disselenetos e diteluretos de diorganoíla, mas ineficaz com dissulfetos de diorganoíla. Através desta metodologia, obtiveram-se 27 novas moléculas inéditas com rendimentos que variaram de 21 a 84%. Além disso, as 2-(organocalcogenil)-indolizinas obtidas foram facilmente transformadas em produtos mais complexos usando reações em condições de acoplamento cruzado do tipo Suzuki catalisada por sais de paládio com ácidos borônicos. Condição a qual forneceu 3 novos exemplos das 2-arilindolizinas com rendimentos de 38 a 73%.Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqporUniversidade 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/openAccessCobreHeterociclosIndolizinasSelenetosSelênioTelúrioCopperHeterocyclesIndolizinesSelenidesSeleniumTelluriumCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAFormação de ligações carbono-nitrogênio e carbonocalcogênio catalisadas por iodeto de cobre: síntese de 2- (organocalcogenil)-indolizinasCopper iodide-catalyzed carbon-nitrogen carbon-chalcogen bonds formation: synthesis of 2-(organochalcogenyl)- indolizinesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisZeni, Gilson Rogériohttp://lattes.cnpq.br/2355575631197937Dornelles, Lucianohttp://lattes.cnpq.br/7629319262073140Campos, Patrick Teixeirahttp://lattes.cnpq.br/9549998755426589http://lattes.cnpq.br/0845333536501990Goulart, Tales Antonio Camargo100600000000600b21a898a-0ab0-4f33-b980-2b55ef590b94f9a9f23d-b66d-4cd0-a042-9effcb02b3897dfea8f7-fe97-4100-9d09-8f5a40fe231689e21349-4fbd-4166-b4c7-8536cd59e133reponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMCC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; 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dc.title.por.fl_str_mv |
Formação de ligações carbono-nitrogênio e carbonocalcogênio catalisadas por iodeto de cobre: síntese de 2- (organocalcogenil)-indolizinas |
dc.title.alternative.eng.fl_str_mv |
Copper iodide-catalyzed carbon-nitrogen carbon-chalcogen bonds formation: synthesis of 2-(organochalcogenyl)- indolizines |
title |
Formação de ligações carbono-nitrogênio e carbonocalcogênio catalisadas por iodeto de cobre: síntese de 2- (organocalcogenil)-indolizinas |
spellingShingle |
Formação de ligações carbono-nitrogênio e carbonocalcogênio catalisadas por iodeto de cobre: síntese de 2- (organocalcogenil)-indolizinas Goulart, Tales Antonio Camargo Cobre Heterociclos Indolizinas Selenetos Selênio Telúrio Copper Heterocycles Indolizines Selenides Selenium Tellurium CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Formação de ligações carbono-nitrogênio e carbonocalcogênio catalisadas por iodeto de cobre: síntese de 2- (organocalcogenil)-indolizinas |
title_full |
Formação de ligações carbono-nitrogênio e carbonocalcogênio catalisadas por iodeto de cobre: síntese de 2- (organocalcogenil)-indolizinas |
title_fullStr |
Formação de ligações carbono-nitrogênio e carbonocalcogênio catalisadas por iodeto de cobre: síntese de 2- (organocalcogenil)-indolizinas |
title_full_unstemmed |
Formação de ligações carbono-nitrogênio e carbonocalcogênio catalisadas por iodeto de cobre: síntese de 2- (organocalcogenil)-indolizinas |
title_sort |
Formação de ligações carbono-nitrogênio e carbonocalcogênio catalisadas por iodeto de cobre: síntese de 2- (organocalcogenil)-indolizinas |
author |
Goulart, Tales Antonio Camargo |
author_facet |
Goulart, Tales Antonio Camargo |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Zeni, Gilson Rogério |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/2355575631197937 |
dc.contributor.referee1.fl_str_mv |
Dornelles, Luciano |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/7629319262073140 |
dc.contributor.referee2.fl_str_mv |
Campos, Patrick Teixeira |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/9549998755426589 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/0845333536501990 |
dc.contributor.author.fl_str_mv |
Goulart, Tales Antonio Camargo |
contributor_str_mv |
Zeni, Gilson Rogério Dornelles, Luciano Campos, Patrick Teixeira |
dc.subject.por.fl_str_mv |
Cobre Heterociclos Indolizinas Selenetos Selênio Telúrio |
topic |
Cobre Heterociclos Indolizinas Selenetos Selênio Telúrio Copper Heterocycles Indolizines Selenides Selenium Tellurium CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Copper Heterocycles Indolizines Selenides Selenium Tellurium |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
The copper-catalyzed cyclization of propargylpyridines with diorganyl dichalcogenides was applied to the synthesis of 2-(organochalcogenyl)-indolizines. A systematic study of the cyclization system revealed that the mutual action between copper(I) iodide and diorganyl dichalcogenides is essential for the formation of 2- (organochalcogenyl)-indolizines in good yields avoiding the formation of hydrogenated indolizine. The standard reactional conditions with the use of propargylpyridines (0.25 mmol), diorganyl dichalcogenides (0.375 mmol), copper (I) Iodide (20 mol%), sodium carbonate (0.50 mmol) in DMF (3 mL) were compatible with many replacements in the substrate, such as methyl, chlorine, fluoride, methoxyl and trifluoromethyl. This protocol was efficient with diorganyl diselenides and ditellurides but ineffective with diorganyl disulfides. Through this methodology, 27 new molecules were obtained with yields ranging from 21 to 84%. In addition, the 2- (organochalcogenyl)-Indolizines obtained were easily transformed into more complex products using reactions in cross-coupling conditions of the Suzuki type catalyzed by palladium salts with bronic acids. Condition which provided 3 new examples of the 2- aryl-indolizinas with yields of 38 to 73%. |
publishDate |
2018 |
dc.date.issued.fl_str_mv |
2018-02-28 |
dc.date.accessioned.fl_str_mv |
2019-02-12T10:51:48Z |
dc.date.available.fl_str_mv |
2019-02-12T10:51:48Z |
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.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/15602 |
url |
http://repositorio.ufsm.br/handle/1/15602 |
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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