Hidrotiolação regio e estereosseletiva de sistemas diínos: síntese e reatividade de (Z)-tioeninos

Detalhes bibliográficos
Ano de defesa: 2022
Autor(a) principal: Welter, Luiz Eduardo lattes
Orientador(a): Zeni, Gilson Rogério lattes
Banca de defesa: Botteselle, Giancarlo Di Vaccari, Azeredo, Juliano Braun de
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:
Tioeninos
Tiol
Tiolato
Sulfetos vinílicos
Eninos
Alcinos
Palavras-chave em Inglês:
Thioenynes
Thiolate
Vinyl sulfides
Enynes
Alkynes
Área do conhecimento CNPq:
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
Link de acesso: http://repositorio.ufsm.br/handle/1/24117
Resumo: Sulfur compounds are important building blocks in Organic Chemistry. The class of vinyl sulfides stands out for its versatility and applicability in the synthesis of new structures. Due to the relevance of these compounds, we intend to find a new methodology for the regio and stereoselective synthesis of (Z)-thioenynes a direct hydrothiolation of conjugated 1,3-diynes promoted by lithium thiolate. A systematic study of the reaction conditions revealed that the presence of ethanol played an essential role in obtaining (Z)-thioenyne compounds with yields between 50 and 93%. The standard reaction conditions were compatible with different functional groups in the substrates, such as alkyl and propargyl alcohols, as well as aryl variations with electron-withdrawing and electron-donating groups. Based on the data obtained, we verified that in this hydrothiolation reaction, lithium thiolate, formed by the reaction n-butyllithium with elemental sulfur, promotes an anti-pathway addition to carbon-carbon triple bond and the concomitant trapping of hydrogen from ethanol by the formed vinyl anion. The (Z)-thioenynes obtained by the described method proved to be versatile substrates for the synthesis of functionalized thiophenes through copper-catalyzed electrophilic cyclization reactions with diphenyl diselenide.
id UFSM_e851c0d1cbb08ba9b5f4da7f2aebb185
oai_identifier_str oai:repositorio.ufsm.br:1/24117
network_acronym_str UFSM
network_name_str Biblioteca Digital de Teses e Dissertações do UFSM
repository_id_str
spelling 2022-04-20T17:19:27Z2022-04-20T17:19:27Z2022-03-10http://repositorio.ufsm.br/handle/1/24117Sulfur compounds are important building blocks in Organic Chemistry. The class of vinyl sulfides stands out for its versatility and applicability in the synthesis of new structures. Due to the relevance of these compounds, we intend to find a new methodology for the regio and stereoselective synthesis of (Z)-thioenynes a direct hydrothiolation of conjugated 1,3-diynes promoted by lithium thiolate. A systematic study of the reaction conditions revealed that the presence of ethanol played an essential role in obtaining (Z)-thioenyne compounds with yields between 50 and 93%. The standard reaction conditions were compatible with different functional groups in the substrates, such as alkyl and propargyl alcohols, as well as aryl variations with electron-withdrawing and electron-donating groups. Based on the data obtained, we verified that in this hydrothiolation reaction, lithium thiolate, formed by the reaction n-butyllithium with elemental sulfur, promotes an anti-pathway addition to carbon-carbon triple bond and the concomitant trapping of hydrogen from ethanol by the formed vinyl anion. The (Z)-thioenynes obtained by the described method proved to be versatile substrates for the synthesis of functionalized thiophenes through copper-catalyzed electrophilic cyclization reactions with diphenyl diselenide.Compostos sulfurados são importantes blocos construtores em Química Orgânica. A classe dos sulfetos vinílicos se destacam pela sua versatilidade e aplicabilidade na síntese de novas estruturas. Devido a relevância destes compostos, buscamos encontrar uma nova metodologia para a síntese regio e estereosseletiva de (Z)-tioeninos a partir de reações de hidrotiolação direta de 1,3-diínos conjugados promovida por tiolato de lítio. Um estudo sistemático das condições reacionais revelou que a presença de etanol desempenha um papel essencial para obtenção dos compostos (Z)-tioeninos com rendimentos entre 50 a 93%. As condições de reação padrão foram compatíveis com distintos grupos funcionais nos substratos, como álcoois alquílicos e propargílicos além de variações arílicas com grupos doadores e retirados de densidade eletrônica. Com base nos dados obtidos, verificamos que nesta reação de hidrotiolação, o tiolato de lítio, formado a partir da reação de n-butil lítio com enxofre elementar, promove uma adição anti à ligação tripla carbono-carbono e o concomitante aprisionamento do hidrogênio do etanol pelo ânion vinil formado. Os (Z)-tioeninos obtidos pelo método descrito provaram ser substratos versáteis para a síntese de tiofenos funcionalizados através de reações de ciclização eletrofílica catalisadas por cobre com disseleneto de difenila.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/openAccessTioeninosTiolTiolatoSulfetos vinílicosEninosAlcinosThioenynesThiolateVinyl sulfidesEnynesAlkynesCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAHidrotiolação regio e estereosseletiva de sistemas diínos: síntese e reatividade de (Z)-tioeninosRegio and stereoselective hydrothiolation of diyne systems: synthesis and reactivity of (Z)-thioenyneinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisZeni, Gilson Rogériohttp://lattes.cnpq.br/2355575631197937Dornelles, LucianoBotteselle, Giancarlo Di VaccariAzeredo, Juliano Braun dehttp://lattes.cnpq.br/4855810204182910Welter, Luiz Eduardo100600000000600600600600600600b21a898a-0ab0-4f33-b980-2b55ef590b94cc29da43-4378-4e3f-9bac-6ead3c0584c988ff8616-1678-47c5-b3c5-9a8e5085844f0b8dde9d-0e12-4bf7-93df-dc116b148a69dc457fc7-62e6-4916-a75f-60ff5f812f97reponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALDIS_PPGQUÍMICA_2022_WELTER_LUIZ.pdfDIS_PPGQUÍMICA_2022_WELTER_LUIZ.pdfDissertação de mestradoapplication/pdf6389094http://repositorio.ufsm.br/bitstream/1/24117/1/DIS_PPGQU%c3%8dMICA_2022_WELTER_LUIZ.pdf4f8caae0b21b8c09112f35b8e634a667MD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8805http://repositorio.ufsm.br/bitstream/1/24117/2/license_rdf4460e5956bc1d1639be9ae6146a50347MD52LICENSElicense.txtlicense.txttext/plain; charset=utf-81956http://repositorio.ufsm.br/bitstream/1/24117/3/license.txt2f0571ecee68693bd5cd3f17c1e075dfMD531/241172022-04-20 14:19:27.465oai:repositorio.ufsm.br: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 Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2022-04-20T17:19:27Biblioteca Digital de Teses e Dissertações do UFSM - Universidade Federal de Santa Maria (UFSM)false
dc.title.por.fl_str_mv Hidrotiolação regio e estereosseletiva de sistemas diínos: síntese e reatividade de (Z)-tioeninos
dc.title.alternative.eng.fl_str_mv Regio and stereoselective hydrothiolation of diyne systems: synthesis and reactivity of (Z)-thioenyne
title Hidrotiolação regio e estereosseletiva de sistemas diínos: síntese e reatividade de (Z)-tioeninos
spellingShingle Hidrotiolação regio e estereosseletiva de sistemas diínos: síntese e reatividade de (Z)-tioeninos
Welter, Luiz Eduardo
Tioeninos
Tiol
Tiolato
Sulfetos vinílicos
Eninos
Alcinos
Thioenynes
Thiolate
Vinyl sulfides
Enynes
Alkynes
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
title_short Hidrotiolação regio e estereosseletiva de sistemas diínos: síntese e reatividade de (Z)-tioeninos
title_full Hidrotiolação regio e estereosseletiva de sistemas diínos: síntese e reatividade de (Z)-tioeninos
title_fullStr Hidrotiolação regio e estereosseletiva de sistemas diínos: síntese e reatividade de (Z)-tioeninos
title_full_unstemmed Hidrotiolação regio e estereosseletiva de sistemas diínos: síntese e reatividade de (Z)-tioeninos
title_sort Hidrotiolação regio e estereosseletiva de sistemas diínos: síntese e reatividade de (Z)-tioeninos
author Welter, Luiz Eduardo
author_facet Welter, Luiz Eduardo
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.advisor-co1.fl_str_mv Dornelles, Luciano
dc.contributor.referee1.fl_str_mv Botteselle, Giancarlo Di Vaccari
dc.contributor.referee2.fl_str_mv Azeredo, Juliano Braun de
dc.contributor.authorLattes.fl_str_mv http://lattes.cnpq.br/4855810204182910
dc.contributor.author.fl_str_mv Welter, Luiz Eduardo
contributor_str_mv Zeni, Gilson Rogério
Dornelles, Luciano
Botteselle, Giancarlo Di Vaccari
Azeredo, Juliano Braun de
dc.subject.por.fl_str_mv Tioeninos
Tiol
Tiolato
Sulfetos vinílicos
Eninos
Alcinos
topic Tioeninos
Tiol
Tiolato
Sulfetos vinílicos
Eninos
Alcinos
Thioenynes
Thiolate
Vinyl sulfides
Enynes
Alkynes
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
dc.subject.eng.fl_str_mv Thioenynes
Thiolate
Vinyl sulfides
Enynes
Alkynes
dc.subject.cnpq.fl_str_mv CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
description Sulfur compounds are important building blocks in Organic Chemistry. The class of vinyl sulfides stands out for its versatility and applicability in the synthesis of new structures. Due to the relevance of these compounds, we intend to find a new methodology for the regio and stereoselective synthesis of (Z)-thioenynes a direct hydrothiolation of conjugated 1,3-diynes promoted by lithium thiolate. A systematic study of the reaction conditions revealed that the presence of ethanol played an essential role in obtaining (Z)-thioenyne compounds with yields between 50 and 93%. The standard reaction conditions were compatible with different functional groups in the substrates, such as alkyl and propargyl alcohols, as well as aryl variations with electron-withdrawing and electron-donating groups. Based on the data obtained, we verified that in this hydrothiolation reaction, lithium thiolate, formed by the reaction n-butyllithium with elemental sulfur, promotes an anti-pathway addition to carbon-carbon triple bond and the concomitant trapping of hydrogen from ethanol by the formed vinyl anion. The (Z)-thioenynes obtained by the described method proved to be versatile substrates for the synthesis of functionalized thiophenes through copper-catalyzed electrophilic cyclization reactions with diphenyl diselenide.
publishDate 2022
dc.date.accessioned.fl_str_mv 2022-04-20T17:19:27Z
dc.date.available.fl_str_mv 2022-04-20T17:19:27Z
dc.date.issued.fl_str_mv 2022-03-10
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/1/24117
url http://repositorio.ufsm.br/handle/1/24117
dc.language.iso.fl_str_mv por
language por
dc.relation.cnpq.fl_str_mv 100600000000
dc.relation.confidence.fl_str_mv 600
600
600
600
600
600
dc.relation.authority.fl_str_mv b21a898a-0ab0-4f33-b980-2b55ef590b94
cc29da43-4378-4e3f-9bac-6ead3c0584c9
88ff8616-1678-47c5-b3c5-9a8e5085844f
0b8dde9d-0e12-4bf7-93df-dc116b148a69
dc457fc7-62e6-4916-a75f-60ff5f812f97
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:Biblioteca Digital de Teses e Dissertações do UFSM
instname:Universidade Federal de Santa Maria (UFSM)
instacron:UFSM
instname_str Universidade Federal de Santa Maria (UFSM)
instacron_str UFSM
institution UFSM
reponame_str Biblioteca Digital de Teses e Dissertações do UFSM
collection Biblioteca Digital de Teses e Dissertações do UFSM
bitstream.url.fl_str_mv http://repositorio.ufsm.br/bitstream/1/24117/1/DIS_PPGQU%c3%8dMICA_2022_WELTER_LUIZ.pdf
http://repositorio.ufsm.br/bitstream/1/24117/2/license_rdf
http://repositorio.ufsm.br/bitstream/1/24117/3/license.txt
bitstream.checksum.fl_str_mv 4f8caae0b21b8c09112f35b8e634a667
4460e5956bc1d1639be9ae6146a50347
2f0571ecee68693bd5cd3f17c1e075df
bitstream.checksumAlgorithm.fl_str_mv MD5
MD5
MD5
repository.name.fl_str_mv Biblioteca Digital de Teses e Dissertações do UFSM - Universidade Federal de Santa Maria (UFSM)
repository.mail.fl_str_mv atendimento.sib@ufsm.br||tedebc@gmail.com
_version_ 1793240062994939904

Registros relacionados