Formação de ligações carbono-nitrogênio e carbonocalcogênio catalisadas por iodeto de cobre: síntese de 2- (organocalcogenil)-indolizinas

Detalhes bibliográficos
Ano de defesa: 2018
Autor(a) principal: Goulart, Tales Antonio Camargo lattes
Orientador(a): Zeni, Gilson Rogério lattes
Banca de defesa: Dornelles, Luciano lattes, Campos, Patrick Teixeira lattes
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:
Cobre
Heterociclos
Indolizinas
Selenetos
Selênio
Telúrio
Palavras-chave em Inglês:
Copper
Heterocycles
Indolizines
Selenides
Selenium
Tellurium
Área do conhecimento CNPq:
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
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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spelling 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:Manancial - Repositório Digital da 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
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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 reponame:Manancial - Repositório Digital da UFSM
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