Síntese de 2-alquinil telurofenos via reação de sonogashira entre 2-halotelurofeno e 1-alcinos
Autor(a) principal: | |
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Data de Publicação: | 2006 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Manancial - Repositório Digital da UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/4295 |
Resumo: | We present herein our results of the palladium-catalyzed cross-coupling of 2-halotellurophenes with several terminal alkynes to give acetylenic tellurophene derivatives in excellent yields. Our initial efforts were devoted to the selection of a suitable catalyst system for efficient Sonogashira coupling reaction between 2-halotellurophenes and terminal alkynes. To this end 2-iodo-5-butyl-tellurophenes and propargyl alcohols were treated at room temperature, with Pd(0) and Pd(II) catalysts, in the presence or in the absence of CuI, Et3N and using different solvents. Thus, PdCl2(PPh3)2, CuI , THF and Et3N at room temperature for 12 h was chosen as the optimum condition for this coupling reaction. In order to demonstrate the efficiency of this reaction, we explored the generality of our method extending the conditions to other terminal alkynes and the products were obtained in good yields (54 - 98%). Concerning the structure of tellurophenes, we found that both butyl and phenyl iodotellurophenes were suitable for in this methodology. After the reaction conditions for 2-iodotellurophenes have been optimized, we turned our attention to 2-bromotellurophenes. Thus, extending the standard catalytic system, used to the coupling reaction described for 2-iodotellurophenes, to the reaction of 2-bromotellurophenes with terminal alkynes it was possible to obtain the desired products in lower yields (38 - 66%). Toxicological and pharmacological activities of these compounds are under study in our laboratory. Compounds A and B at 300 mM reduced lipid peroxidation about 30% and did not present thiol-oxidase activity. d-Aminolevulinate dehydratase (d-ALA-D) activity, an enzyme sensible to organochacogen compounds, was inhibited by 300 mM of compound B (about 35%), conversely compound A did not change the enzyme activity. Additionally, previous studies of the reaction conditions between 2- butyltelluro-tellurophenes and terminal alkynes resulted in the corresponding cross coupled product in moderate yield (66%), indicating the viability of these compounds as substrates in Sonogashira reactions. |
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Síntese de 2-alquinil telurofenos via reação de sonogashira entre 2-halotelurofeno e 1-alcinosSynthesis of 2-acetylenic tellurophenes via sonogashira s reaction between 2-halotellurophenes and 1-alkynesQuímicaCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAWe present herein our results of the palladium-catalyzed cross-coupling of 2-halotellurophenes with several terminal alkynes to give acetylenic tellurophene derivatives in excellent yields. Our initial efforts were devoted to the selection of a suitable catalyst system for efficient Sonogashira coupling reaction between 2-halotellurophenes and terminal alkynes. To this end 2-iodo-5-butyl-tellurophenes and propargyl alcohols were treated at room temperature, with Pd(0) and Pd(II) catalysts, in the presence or in the absence of CuI, Et3N and using different solvents. Thus, PdCl2(PPh3)2, CuI , THF and Et3N at room temperature for 12 h was chosen as the optimum condition for this coupling reaction. In order to demonstrate the efficiency of this reaction, we explored the generality of our method extending the conditions to other terminal alkynes and the products were obtained in good yields (54 - 98%). Concerning the structure of tellurophenes, we found that both butyl and phenyl iodotellurophenes were suitable for in this methodology. After the reaction conditions for 2-iodotellurophenes have been optimized, we turned our attention to 2-bromotellurophenes. Thus, extending the standard catalytic system, used to the coupling reaction described for 2-iodotellurophenes, to the reaction of 2-bromotellurophenes with terminal alkynes it was possible to obtain the desired products in lower yields (38 - 66%). Toxicological and pharmacological activities of these compounds are under study in our laboratory. Compounds A and B at 300 mM reduced lipid peroxidation about 30% and did not present thiol-oxidase activity. d-Aminolevulinate dehydratase (d-ALA-D) activity, an enzyme sensible to organochacogen compounds, was inhibited by 300 mM of compound B (about 35%), conversely compound A did not change the enzyme activity. Additionally, previous studies of the reaction conditions between 2- butyltelluro-tellurophenes and terminal alkynes resulted in the corresponding cross coupled product in moderate yield (66%), indicating the viability of these compounds as substrates in Sonogashira reactions.Neste trabalho estudamos as condições para uma reação de acoplamento entre derivados de telurofeno 2-halo substituídos com acetilenos terminais sob catálise de paládio em meio básico objetivando a síntese de 2-alquinil telurofenos. O estudo de otimização das condições reacionais foi realizado promovendo o acoplamento entre o álcool propargílico e o 2-iodo-5-butiltelurofeno, alternandose as variáveis amina, estado de oxidação do catalisador de paládio, presença do co-catalisador CuI e solvente utilizado. Optou-se pelo sistema utilizando Et3N, Pd(PPh3)2Cl2 como catalisador na presença do co-catalisador CuI em THF. A influência da substituição na posição 5 do telurofeno foi verificada, alternando entre 2-iodo-5-butiltelurofeno e 2-iodo-5-feniltelurofenos. A reação nas condições escolhidas mostrou-se pouco sensível a substituição nesta posição para os substituintes estudados. Deste estudo resultou uma série de produtos de acoplamento entre os telurofeno 2-iodo substituídos com acetilenos terminais com rendimentos entre 54 e 98%. A reatividade dos halotelurofenos foi verificada ao promover-se a reação entre 2-bromotelurofenos e uma série representativa de alcinos terminais. Os telurofenos 2-bromo substituídos mostraram-se menos reativos levando aos produtos de acoplamento em menores rendimentos entre 38 e 66%. Dois telurofenos tiveram seus efeitos avaliados em ensaios farmacológicos e toxicológicos in vitro. Seus efeitos foram observados em ensaios de peroxidação lipídica e dosagem da atividade da enzima d-Aminolevulinato desidratase (d-ALAD), uma enzima sensível a compostos organocalcogênios. A atividade tiol oxidase foi examinada para avaliar a propriedade pró-oxidante desses compostos. Te Ph Te Ph HO OH A B Os compostos A e B reduziram os níveis de peroxidação lipídica a partir de 300 mM em torno de 30%. Entretanto, os dois compostos testados não apresentaram atividade tiol oxidase. A atividade da enzima d-ALA-D foi inibida pelo composto B na concentração de 300 mM em torno de 35%, ao contrário do composto A que não alterou a atividade da enzima d-ALA-D. Complementarmente, estudos prévios das condições reacionais para acoplamento entre 2-butiltelurotelurofeno e 1-alcinos foram realizados e indicam a viabilidade destes compostos como substratos em reações de Sonogashira.Universidade Federal de Santa MariaBRQuímicaUFSMPrograma de Pós-Graduação em QuímicaZeni, Gilson Rogériohttp://lattes.cnpq.br/2355575631197937Dornelles, Lucianohttp://lattes.cnpq.br/7629319262073140Braga, Antonio Luizhttp://lattes.cnpq.br/0314009951286457Rodrigues, Oscar Endrigo Dorneleshttp://lattes.cnpq.br/6536519955416085Jacob, Raquel Guimarãeshttp://lattes.cnpq.br/0978329001891199Panatieri, Rodrigo Barroso2017-05-222017-05-222006-05-29info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfapplication/pdfPANATIERI, Rodrigo Barroso. Synthesis of 2-acetylenic tellurophenes via sonogashira s reaction between 2-halotellurophenes and 1-alkynes. 2006. 124 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2006.http://repositorio.ufsm.br/handle/1/4295porinfo:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSM2023-01-27T12:10:30Zoai:repositorio.ufsm.br:1/4295Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2023-01-27T12:10:30Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.none.fl_str_mv |
Síntese de 2-alquinil telurofenos via reação de sonogashira entre 2-halotelurofeno e 1-alcinos Synthesis of 2-acetylenic tellurophenes via sonogashira s reaction between 2-halotellurophenes and 1-alkynes |
title |
Síntese de 2-alquinil telurofenos via reação de sonogashira entre 2-halotelurofeno e 1-alcinos |
spellingShingle |
Síntese de 2-alquinil telurofenos via reação de sonogashira entre 2-halotelurofeno e 1-alcinos Panatieri, Rodrigo Barroso Química CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese de 2-alquinil telurofenos via reação de sonogashira entre 2-halotelurofeno e 1-alcinos |
title_full |
Síntese de 2-alquinil telurofenos via reação de sonogashira entre 2-halotelurofeno e 1-alcinos |
title_fullStr |
Síntese de 2-alquinil telurofenos via reação de sonogashira entre 2-halotelurofeno e 1-alcinos |
title_full_unstemmed |
Síntese de 2-alquinil telurofenos via reação de sonogashira entre 2-halotelurofeno e 1-alcinos |
title_sort |
Síntese de 2-alquinil telurofenos via reação de sonogashira entre 2-halotelurofeno e 1-alcinos |
author |
Panatieri, Rodrigo Barroso |
author_facet |
Panatieri, Rodrigo Barroso |
author_role |
author |
dc.contributor.none.fl_str_mv |
Zeni, Gilson Rogério http://lattes.cnpq.br/2355575631197937 Dornelles, Luciano http://lattes.cnpq.br/7629319262073140 Braga, Antonio Luiz http://lattes.cnpq.br/0314009951286457 Rodrigues, Oscar Endrigo Dorneles http://lattes.cnpq.br/6536519955416085 Jacob, Raquel Guimarães http://lattes.cnpq.br/0978329001891199 |
dc.contributor.author.fl_str_mv |
Panatieri, Rodrigo Barroso |
dc.subject.por.fl_str_mv |
Química CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
Química CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
We present herein our results of the palladium-catalyzed cross-coupling of 2-halotellurophenes with several terminal alkynes to give acetylenic tellurophene derivatives in excellent yields. Our initial efforts were devoted to the selection of a suitable catalyst system for efficient Sonogashira coupling reaction between 2-halotellurophenes and terminal alkynes. To this end 2-iodo-5-butyl-tellurophenes and propargyl alcohols were treated at room temperature, with Pd(0) and Pd(II) catalysts, in the presence or in the absence of CuI, Et3N and using different solvents. Thus, PdCl2(PPh3)2, CuI , THF and Et3N at room temperature for 12 h was chosen as the optimum condition for this coupling reaction. In order to demonstrate the efficiency of this reaction, we explored the generality of our method extending the conditions to other terminal alkynes and the products were obtained in good yields (54 - 98%). Concerning the structure of tellurophenes, we found that both butyl and phenyl iodotellurophenes were suitable for in this methodology. After the reaction conditions for 2-iodotellurophenes have been optimized, we turned our attention to 2-bromotellurophenes. Thus, extending the standard catalytic system, used to the coupling reaction described for 2-iodotellurophenes, to the reaction of 2-bromotellurophenes with terminal alkynes it was possible to obtain the desired products in lower yields (38 - 66%). Toxicological and pharmacological activities of these compounds are under study in our laboratory. Compounds A and B at 300 mM reduced lipid peroxidation about 30% and did not present thiol-oxidase activity. d-Aminolevulinate dehydratase (d-ALA-D) activity, an enzyme sensible to organochacogen compounds, was inhibited by 300 mM of compound B (about 35%), conversely compound A did not change the enzyme activity. Additionally, previous studies of the reaction conditions between 2- butyltelluro-tellurophenes and terminal alkynes resulted in the corresponding cross coupled product in moderate yield (66%), indicating the viability of these compounds as substrates in Sonogashira reactions. |
publishDate |
2006 |
dc.date.none.fl_str_mv |
2006-05-29 2017-05-22 2017-05-22 |
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 |
PANATIERI, Rodrigo Barroso. Synthesis of 2-acetylenic tellurophenes via sonogashira s reaction between 2-halotellurophenes and 1-alkynes. 2006. 124 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2006. http://repositorio.ufsm.br/handle/1/4295 |
identifier_str_mv |
PANATIERI, Rodrigo Barroso. Synthesis of 2-acetylenic tellurophenes via sonogashira s reaction between 2-halotellurophenes and 1-alkynes. 2006. 124 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2006. |
url |
http://repositorio.ufsm.br/handle/1/4295 |
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_ |
1805922065938644992 |