Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização Intramolecular
Autor(a) principal: | |
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Data de Publicação: | 2013 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Manancial - Repositório Digital da UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/4254 |
Resumo: | In the first part of this work, a series of selenophenes and tellurophenes were prepared starting from of (Z)-chalcogenoenynes, by employing FeCl3 diorganyl dichalcogenide-mediated intramolecular cyclization. In general, the cyclic products were obtained in moderate to good yields. In order to evaluate the versatility of the obtained 3-chalcogen selenophene derivatives, we tested the reactivity of these compounds toward halogenation and Li/Se exchange reactions. In this way, the reaction of 2,5-diphenil-3-(fenilselene)-selenofene with an excess of bromine, afforded the resultant product in 86% yield. In addition, the reaction of 2,5-diphenil-3-(butilselene)selenofene with n-butyllithium gave the lithiated species. The lithiated species was trapped by aldehydes affording the secondary alcohols in 68 to 73% yield. In a second stage, we developed an alternative method to promote the intramolecular cyclization of o-alkynyl benzaldimines 3, by employing CuI and differently substituted diorganoyl diselenides as promoter agents of this process. Through this cyclization protocol we could satisfactory synthesize a series of 4-organochalcogen-isoquinolines 4 in good yields. Finally, the presence of an organochalcogen substituent in the isoquinoline structure allowed further structural elaboration through conversion of the chalcogen group into other substituents. In this sense, when the 4-(buthyltelluro)-3-phenylisoquinoline was applied to the tellurium lithium exchange conditions, followed by reaction with aldehydes, the corresponding secondary alcohols were obtained in high yields. Furthermore, we have also successfully applied this isoquinoline as a substrate in Suzuki and Sonogashira coupling conditions affording the corresponding products moderate to good yields. |
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Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização IntramolecularSynthesis of Chalcogenophenes and Isoquinolines by Intramolecular Cyclization ReactionsQuímicaHeterociclosCalcogenofenosDicalcogenetosQuímica orgânicaCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAIn the first part of this work, a series of selenophenes and tellurophenes were prepared starting from of (Z)-chalcogenoenynes, by employing FeCl3 diorganyl dichalcogenide-mediated intramolecular cyclization. In general, the cyclic products were obtained in moderate to good yields. In order to evaluate the versatility of the obtained 3-chalcogen selenophene derivatives, we tested the reactivity of these compounds toward halogenation and Li/Se exchange reactions. In this way, the reaction of 2,5-diphenil-3-(fenilselene)-selenofene with an excess of bromine, afforded the resultant product in 86% yield. In addition, the reaction of 2,5-diphenil-3-(butilselene)selenofene with n-butyllithium gave the lithiated species. The lithiated species was trapped by aldehydes affording the secondary alcohols in 68 to 73% yield. In a second stage, we developed an alternative method to promote the intramolecular cyclization of o-alkynyl benzaldimines 3, by employing CuI and differently substituted diorganoyl diselenides as promoter agents of this process. Through this cyclization protocol we could satisfactory synthesize a series of 4-organochalcogen-isoquinolines 4 in good yields. Finally, the presence of an organochalcogen substituent in the isoquinoline structure allowed further structural elaboration through conversion of the chalcogen group into other substituents. In this sense, when the 4-(buthyltelluro)-3-phenylisoquinoline was applied to the tellurium lithium exchange conditions, followed by reaction with aldehydes, the corresponding secondary alcohols were obtained in high yields. Furthermore, we have also successfully applied this isoquinoline as a substrate in Suzuki and Sonogashira coupling conditions affording the corresponding products moderate to good yields.Coordenação de Aperfeiçoamento de Pessoal de Nível SuperiorEste trabalho relata a síntese de uma série de heterociclos através da ciclização intramolecular de substratos alquinílicos com dicalcogenetos de diorganoíla mediados por sais de cobre ou sais de ferro. Primeiramente, relatamos a síntese de selenofenos e telurofenos 2 através da ciclização intramolecular de (Z)-selenoeninos e (Z)-teluroeninos 1 com dicalcogenetos de diorganoíla mediados por FeCl3. Essa metodologia permitiu a obtenção de novos derivados de calcogenofenos de moderados a bons rendimentos com a adicional inserção de uma molécula orgânica de calcogênio na posição 3 do anel formado. Com a finalidade de avaliar o potencial reatividade dos compostos obtidos 2, o composto 2,5-difenil-3-(selenofenil)-selenofeno foi submetido a uma reação de bromação do anel aromático resultando na formação do selenofeno substituído com bromo, nas posições 3 e 4 do anel heterocíclico, em 86% de rendimento. Adicionalmente, o composto 2,5-difenil-3-(selenobutil)selenofeno foi selecionado como material de partida para uma reação de troca selênio-lítio com a subsequente reação com aldeídos levando a formação dos álcoois secundários, na posição 3 do anel do selenofeno, em rendimentos de 68-73%. Posteriormente, desenvolvemos uma metodologia para síntese de 4-organocalcogeno-isoquinolinas 4, partindo-se dos substratos o-alquinil benzaldiminas 3. A combinação de quantidades catalíticas de CuI com dicalcogenetos de diorganoíla mostrou-se eficiente para obtenção das isoquinolinas em bons rendimentos A fim de avaliar a versatilidade das 4-organocalcogeno isoquinolinas obtidas, como precursores para síntese de isoquinolinas com diferentes funcionalizações, o composto 4-(telurobutil)-3-fenilisoquinolina foi submetido a reações de acoplamento cruzado do tipo Suzuki e do tipo Sonogashira, catalizados por sais de paládio. Também, foram realizadas as reações de troca telúrio-lítio com a subsequente reação com diferentes aldeídos levando aos alcoóis derivados em bons rendimentos.Universidade Federal de Santa MariaBRQuímicaUFSMPrograma de Pós-Graduação em QuímicaZeni, Gilson Rogériohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4728651J6Cunha, Rodrigo Luiz Oliveira Rodrigueshttp://lattes.cnpq.br/1982300219137583Perin, Gelsonhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797983H8Morel, Ademir Fariashttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783930A8Lenardao, Eder Joaohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4723709P2Stein, André Luiz Agnes2014-10-292014-10-292013-11-26info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfapplication/pdfSTEIN, André Luiz Agnes. Synthesis of Chalcogenophenes and Isoquinolines by Intramolecular Cyclization Reactions. 2013. 188 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013.http://repositorio.ufsm.br/handle/1/4254porinfo:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSM2017-07-25T14:05:10Zoai:repositorio.ufsm.br:1/4254Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2017-07-25T14:05:10Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.none.fl_str_mv |
Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização Intramolecular Synthesis of Chalcogenophenes and Isoquinolines by Intramolecular Cyclization Reactions |
title |
Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização Intramolecular |
spellingShingle |
Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização Intramolecular Stein, André Luiz Agnes Química Heterociclos Calcogenofenos Dicalcogenetos Química orgânica CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização Intramolecular |
title_full |
Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização Intramolecular |
title_fullStr |
Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização Intramolecular |
title_full_unstemmed |
Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização Intramolecular |
title_sort |
Síntese de Calcogenofenos e Isoquinolinas via Reações de Ciclização Intramolecular |
author |
Stein, André Luiz Agnes |
author_facet |
Stein, André Luiz Agnes |
author_role |
author |
dc.contributor.none.fl_str_mv |
Zeni, Gilson Rogério http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4728651J6 Cunha, Rodrigo Luiz Oliveira Rodrigues http://lattes.cnpq.br/1982300219137583 Perin, Gelson http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797983H8 Morel, Ademir Farias http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783930A8 Lenardao, Eder Joao http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4723709P2 |
dc.contributor.author.fl_str_mv |
Stein, André Luiz Agnes |
dc.subject.por.fl_str_mv |
Química Heterociclos Calcogenofenos Dicalcogenetos Química orgânica CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
Química Heterociclos Calcogenofenos Dicalcogenetos Química orgânica CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
In the first part of this work, a series of selenophenes and tellurophenes were prepared starting from of (Z)-chalcogenoenynes, by employing FeCl3 diorganyl dichalcogenide-mediated intramolecular cyclization. In general, the cyclic products were obtained in moderate to good yields. In order to evaluate the versatility of the obtained 3-chalcogen selenophene derivatives, we tested the reactivity of these compounds toward halogenation and Li/Se exchange reactions. In this way, the reaction of 2,5-diphenil-3-(fenilselene)-selenofene with an excess of bromine, afforded the resultant product in 86% yield. In addition, the reaction of 2,5-diphenil-3-(butilselene)selenofene with n-butyllithium gave the lithiated species. The lithiated species was trapped by aldehydes affording the secondary alcohols in 68 to 73% yield. In a second stage, we developed an alternative method to promote the intramolecular cyclization of o-alkynyl benzaldimines 3, by employing CuI and differently substituted diorganoyl diselenides as promoter agents of this process. Through this cyclization protocol we could satisfactory synthesize a series of 4-organochalcogen-isoquinolines 4 in good yields. Finally, the presence of an organochalcogen substituent in the isoquinoline structure allowed further structural elaboration through conversion of the chalcogen group into other substituents. In this sense, when the 4-(buthyltelluro)-3-phenylisoquinoline was applied to the tellurium lithium exchange conditions, followed by reaction with aldehydes, the corresponding secondary alcohols were obtained in high yields. Furthermore, we have also successfully applied this isoquinoline as a substrate in Suzuki and Sonogashira coupling conditions affording the corresponding products moderate to good yields. |
publishDate |
2013 |
dc.date.none.fl_str_mv |
2013-11-26 2014-10-29 2014-10-29 |
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 |
STEIN, André Luiz Agnes. Synthesis of Chalcogenophenes and Isoquinolines by Intramolecular Cyclization Reactions. 2013. 188 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013. http://repositorio.ufsm.br/handle/1/4254 |
identifier_str_mv |
STEIN, André Luiz Agnes. Synthesis of Chalcogenophenes and Isoquinolines by Intramolecular Cyclization Reactions. 2013. 188 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013. |
url |
http://repositorio.ufsm.br/handle/1/4254 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf application/pdf |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria BR Química UFSM Programa de Pós-Graduação em Química |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria BR Química UFSM Programa de Pós-Graduação em Química |
dc.source.none.fl_str_mv |
reponame:Manancial - Repositório Digital da 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 |
Manancial - Repositório Digital da UFSM |
collection |
Manancial - Repositório Digital da UFSM |
repository.name.fl_str_mv |
Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM) |
repository.mail.fl_str_mv |
atendimento.sib@ufsm.br||tedebc@gmail.com |
_version_ |
1805922043113242624 |