Ciclização eletrofílica intramolecular de (Z)-calcogenoeninos: síntese e reatividade de calcogenofenos e (Z)-calcogenetos vinilicos
Ano de defesa: | 2019 |
---|---|
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/1/17172 |
Resumo: | In the present thesis, efficient methods were developed to the synthesis of a series of heterocycles by electrophilic cyclization of (Z)-chalcogenoenynes 1, and chalcogenophenes 2, mediated by species of I2 and/or RSeBr. The first step of this thesis was the synthesis of a series (Z)-chalcogenoenynes 1, via the hydroselenation reaction, and the subsequent cyclization with I2 and/or RSeBr in dichloromethane as solvent and at room temperature. The reaction provided the products in high yields ranging from 28 to 87%. The synthesized products were subjected to coupling type reactions, such as Sonogashira and Suzuki, demonstrating the versatility of chalcogenophenes in the synthesis of different products highly functionalized in yields of 48-68% and 63%. Subsequently, it was possible to synthesize different chemo, stereo and regiosselective (Z)-vinyl chalcogenides, from the nucleophilic substitution reaction promoted by Na2X in the presence of organic halides and terminal alkynes. Through this protocol, it was possible to synthesize, in a satisfactory way (34 to 80% yields), a series of (Z)-vinyl chalcogenides using in situ generated hydroselenation conditions. In order to demonstrate the versatility of the synthesized products in addition to increasing their complexity structure, (Z)-vinyl chalcogenides were used in cross-coupling reactions, such as Suzuki, Kumada and Negishi. |
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Biblioteca Digital de Teses e Dissertações do UFSM |
repository_id_str |
|
spelling |
2019-06-27T13:43:44Z2019-06-27T13:43:44Z2019-02-22http://repositorio.ufsm.br/handle/1/17172In the present thesis, efficient methods were developed to the synthesis of a series of heterocycles by electrophilic cyclization of (Z)-chalcogenoenynes 1, and chalcogenophenes 2, mediated by species of I2 and/or RSeBr. The first step of this thesis was the synthesis of a series (Z)-chalcogenoenynes 1, via the hydroselenation reaction, and the subsequent cyclization with I2 and/or RSeBr in dichloromethane as solvent and at room temperature. The reaction provided the products in high yields ranging from 28 to 87%. The synthesized products were subjected to coupling type reactions, such as Sonogashira and Suzuki, demonstrating the versatility of chalcogenophenes in the synthesis of different products highly functionalized in yields of 48-68% and 63%. Subsequently, it was possible to synthesize different chemo, stereo and regiosselective (Z)-vinyl chalcogenides, from the nucleophilic substitution reaction promoted by Na2X in the presence of organic halides and terminal alkynes. Through this protocol, it was possible to synthesize, in a satisfactory way (34 to 80% yields), a series of (Z)-vinyl chalcogenides using in situ generated hydroselenation conditions. In order to demonstrate the versatility of the synthesized products in addition to increasing their complexity structure, (Z)-vinyl chalcogenides were used in cross-coupling reactions, such as Suzuki, Kumada and Negishi.No presente trabalho desenvolveu-se a síntese eficiente de uma série de heterociclos através da ciclização eletrofílica intramolecular de (Z)-calcogeneninos 1, para a síntese de calcogenofenos 2, mediada por espécies de I2 e/ou RSeBr. Primeiramente, relatamos a síntese de uma série de (Z)-calcogeneninos 1, via reação de hidroselenação, sendo estes, posteriormente ciclizados com I2 e/ou RSeBr em diclorometano como solvente e à temperatura ambiente. A síntese desses produtos se deu de maneira eficiente em rendimentos que variaram de 28% a 87%. Os produtos sintetizados foram ainda submetidos a reações de acoplamento do tipo, sonogashira e suzuki, demonstrando a versatilidade dos calcogenofenos na síntese de produtos diferentes altamente funcionalizados em rendimentos de 48%-68% e 63%. Subsequentemente, foi possível a síntese de diferentes (Z)-calcogenetos vinílicos quimio, estéreo e regiosseletivos, a partir da reação de substituição nucleofílica promovida por Na2X na presença de haletos orgânicos e alquino terminal. Através deste protocolo foi possível sintetizar, de maneira satisfatória (34% a 80% de rendimento), uma série de (Z)-calcogenetos vinílicos utilizando condições de hidroselenação gerado in-situ. Afim de demostrar a versatilidade dos produtos sintetizados além aumentar sua complexidade estrutural, utilizou-se os (Z)-selenetos vinílicos frente a reações de acoplamento cruzado do tipo Suzuki, Kumada e Negishi.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPESporUniversidade 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/openAccessHeterociclosCalcogenofenosEletrofílica(Z)-calcogenetos vinílicosHeterocyclesChalcogenophenesElectrophilicCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICACiclização eletrofílica intramolecular de (Z)-calcogenoeninos: síntese e reatividade de calcogenofenos e (Z)-calcogenetos vinilicosElectrophilic cyclzation intramlecular of (Z)- chalcogenoenynes: synthesis and reactivity of chalcogenophenes and (Z)-vinyl chalconidesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisZeni, Gilson Rogériohttp://lattes.cnpq.br/2355575631197937Iglesias, Bernardo Almeidahttp://lattes.cnpq.br/4402375533322977Godoi, Marcelo dehttp://lattes.cnpq.br/8835435439360229Rodrigues, Oscar Endrigo Dorneleshttp://lattes.cnpq.br/6536519955416085Campos, Patrick Teixeirahttp://lattes.cnpq.br/9549998755426589http://lattes.cnpq.br/1549950446615225Pistoia, Renan Piovesan100600000000600b21a898a-0ab0-4f33-b980-2b55ef590b94fe682264-7ac2-41e6-a0e0-8230087e3108483d6d0c-e419-454b-b413-1a51673258c332c0716a-196c-4165-b607-547a8c2276f0e7f4492f-46f8-436e-b78d-5bee588e11e47b97e671-a249-4a83-8828-600e8cac594ereponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALTES_PPGQUIMICA_2019_PISTOIA_RENAN.pdfTES_PPGQUIMICA_2019_PISTOIA_RENAN.pdfTese de Doutoradoapplication/pdf13912128http://repositorio.ufsm.br/bitstream/1/17172/1/TES_PPGQUIMICA_2019_PISTOIA_RENAN.pdf5d6bfb6a11c188e42bf88550db7a839cMD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; 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dc.title.por.fl_str_mv |
Ciclização eletrofílica intramolecular de (Z)-calcogenoeninos: síntese e reatividade de calcogenofenos e (Z)-calcogenetos vinilicos |
dc.title.alternative.eng.fl_str_mv |
Electrophilic cyclzation intramlecular of (Z)- chalcogenoenynes: synthesis and reactivity of chalcogenophenes and (Z)-vinyl chalconides |
title |
Ciclização eletrofílica intramolecular de (Z)-calcogenoeninos: síntese e reatividade de calcogenofenos e (Z)-calcogenetos vinilicos |
spellingShingle |
Ciclização eletrofílica intramolecular de (Z)-calcogenoeninos: síntese e reatividade de calcogenofenos e (Z)-calcogenetos vinilicos Pistoia, Renan Piovesan Heterociclos Calcogenofenos Eletrofílica (Z)-calcogenetos vinílicos Heterocycles Chalcogenophenes Electrophilic CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Ciclização eletrofílica intramolecular de (Z)-calcogenoeninos: síntese e reatividade de calcogenofenos e (Z)-calcogenetos vinilicos |
title_full |
Ciclização eletrofílica intramolecular de (Z)-calcogenoeninos: síntese e reatividade de calcogenofenos e (Z)-calcogenetos vinilicos |
title_fullStr |
Ciclização eletrofílica intramolecular de (Z)-calcogenoeninos: síntese e reatividade de calcogenofenos e (Z)-calcogenetos vinilicos |
title_full_unstemmed |
Ciclização eletrofílica intramolecular de (Z)-calcogenoeninos: síntese e reatividade de calcogenofenos e (Z)-calcogenetos vinilicos |
title_sort |
Ciclização eletrofílica intramolecular de (Z)-calcogenoeninos: síntese e reatividade de calcogenofenos e (Z)-calcogenetos vinilicos |
author |
Pistoia, Renan Piovesan |
author_facet |
Pistoia, Renan Piovesan |
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 |
Iglesias, Bernardo Almeida |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/4402375533322977 |
dc.contributor.referee2.fl_str_mv |
Godoi, Marcelo de |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/8835435439360229 |
dc.contributor.referee3.fl_str_mv |
Rodrigues, Oscar Endrigo Dorneles |
dc.contributor.referee3Lattes.fl_str_mv |
http://lattes.cnpq.br/6536519955416085 |
dc.contributor.referee4.fl_str_mv |
Campos, Patrick Teixeira |
dc.contributor.referee4Lattes.fl_str_mv |
http://lattes.cnpq.br/9549998755426589 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/1549950446615225 |
dc.contributor.author.fl_str_mv |
Pistoia, Renan Piovesan |
contributor_str_mv |
Zeni, Gilson Rogério Iglesias, Bernardo Almeida Godoi, Marcelo de Rodrigues, Oscar Endrigo Dorneles Campos, Patrick Teixeira |
dc.subject.por.fl_str_mv |
Heterociclos Calcogenofenos Eletrofílica (Z)-calcogenetos vinílicos |
topic |
Heterociclos Calcogenofenos Eletrofílica (Z)-calcogenetos vinílicos Heterocycles Chalcogenophenes Electrophilic CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Heterocycles Chalcogenophenes Electrophilic |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
In the present thesis, efficient methods were developed to the synthesis of a series of heterocycles by electrophilic cyclization of (Z)-chalcogenoenynes 1, and chalcogenophenes 2, mediated by species of I2 and/or RSeBr. The first step of this thesis was the synthesis of a series (Z)-chalcogenoenynes 1, via the hydroselenation reaction, and the subsequent cyclization with I2 and/or RSeBr in dichloromethane as solvent and at room temperature. The reaction provided the products in high yields ranging from 28 to 87%. The synthesized products were subjected to coupling type reactions, such as Sonogashira and Suzuki, demonstrating the versatility of chalcogenophenes in the synthesis of different products highly functionalized in yields of 48-68% and 63%. Subsequently, it was possible to synthesize different chemo, stereo and regiosselective (Z)-vinyl chalcogenides, from the nucleophilic substitution reaction promoted by Na2X in the presence of organic halides and terminal alkynes. Through this protocol, it was possible to synthesize, in a satisfactory way (34 to 80% yields), a series of (Z)-vinyl chalcogenides using in situ generated hydroselenation conditions. In order to demonstrate the versatility of the synthesized products in addition to increasing their complexity structure, (Z)-vinyl chalcogenides were used in cross-coupling reactions, such as Suzuki, Kumada and Negishi. |
publishDate |
2019 |
dc.date.accessioned.fl_str_mv |
2019-06-27T13:43:44Z |
dc.date.available.fl_str_mv |
2019-06-27T13:43:44Z |
dc.date.issued.fl_str_mv |
2019-02-22 |
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/1/17172 |
url |
http://repositorio.ufsm.br/handle/1/17172 |
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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Universidade Federal de Santa Maria (UFSM) |
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UFSM |
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UFSM |
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Biblioteca Digital de Teses e Dissertações do UFSM |
collection |
Biblioteca Digital de Teses e Dissertações do UFSM |
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