Synthesis of fluorescent tetracyclic lactams by a “one pot” three steps palladium-catalyzed borylation, Suzuki coupling (BSC) and lactamization. DNA and polynucleotides binding studies
Autor(a) principal: | |
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Data de Publicação: | 2007 |
Outros Autores: | , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | https://hdl.handle.net/1822/8378 |
Resumo: | Tetracyclic lactams (benzothieno[2,3-c]quinolones) were prepared by “one pot” three steps palladium-catalyzed borylation, Suzuki coupling (BSC) and lactamization, starting from ortho-haloanilines and alkyl 3-bromobenzo[b]thiophene-2-carboxylates. The former were used as the components to be borylated with pinacolborane, and the latter as the brominated component in the Suzuki coupling. The amidation occurred with loss of the alkyl alcohol, presumably in the Suzuki coupling product, giving the corresponding tetracyclic lactam. This constitutes a novel application of the BSC reaction using sterically hindered substrates. In this work studies of absorption and fluorescence in several solvents and in presence of salmon sperm DNA or synthetic double stranded (ds) heteropolynucleotides, poly(dA-dT)•(dA-dT) and poly(dG-dC)•(dG-dC), were performed. The binding constants values (Ki = 2.6x10^5- 4.5x10^5 M^-1) point to a high affinity of the lactams to DNA. It was shown that the intercalation is the prefered mode of binding and that the substituted new lactams (with F or OMe) exhibit a higher affinity for A-T regions. Quenching experiments with iodide show that the methoxylated lactam is the more intercalative in DNA. The same type of experiments using this compound bound to heteropolynucleotides show a very low accessibility (fa = 0.07) of the lactam in poly(dG-dC)•(dG-dC) to the quencher showing a large majority of intercalative binding while the high affinity for A-T regions together with a higher accessiblity (fa = 0.25) point to the possiblity of intercalative and groove binding. |
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Synthesis of fluorescent tetracyclic lactams by a “one pot” three steps palladium-catalyzed borylation, Suzuki coupling (BSC) and lactamization. DNA and polynucleotides binding studiesPalladium-catalyzed BSC reactionLactamizationBenzothieno[2,3-c]quinolonesFluorescenceDNA and polynucleotides bindingpalladiurn-catalyzed BSC reactionbenzothieno[2,3-c]qumolonesScience & TechnologyTetracyclic lactams (benzothieno[2,3-c]quinolones) were prepared by “one pot” three steps palladium-catalyzed borylation, Suzuki coupling (BSC) and lactamization, starting from ortho-haloanilines and alkyl 3-bromobenzo[b]thiophene-2-carboxylates. The former were used as the components to be borylated with pinacolborane, and the latter as the brominated component in the Suzuki coupling. The amidation occurred with loss of the alkyl alcohol, presumably in the Suzuki coupling product, giving the corresponding tetracyclic lactam. This constitutes a novel application of the BSC reaction using sterically hindered substrates. In this work studies of absorption and fluorescence in several solvents and in presence of salmon sperm DNA or synthetic double stranded (ds) heteropolynucleotides, poly(dA-dT)•(dA-dT) and poly(dG-dC)•(dG-dC), were performed. The binding constants values (Ki = 2.6x10^5- 4.5x10^5 M^-1) point to a high affinity of the lactams to DNA. It was shown that the intercalation is the prefered mode of binding and that the substituted new lactams (with F or OMe) exhibit a higher affinity for A-T regions. Quenching experiments with iodide show that the methoxylated lactam is the more intercalative in DNA. The same type of experiments using this compound bound to heteropolynucleotides show a very low accessibility (fa = 0.07) of the lactam in poly(dG-dC)•(dG-dC) to the quencher showing a large majority of intercalative binding while the high affinity for A-T regions together with a higher accessiblity (fa = 0.25) point to the possiblity of intercalative and groove binding.Foundation for the Science and Technology (Portugal) and FEDER for financial support through a research project POCI/QUI/59407/2004 and through Centro de Química and Centro de Física of Univ. Minho.ElsevierUniversidade do MinhoQueiroz, Maria João R. P.Castanheira, Elisabete M. S.Lopes, Teresa C. T.Cruz, Yvonne K.Kirsch, G.2007-032007-03-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/1822/8378eng“Journal of Photochemistry and Photobiology A : Chemistry". ISSN 1010-6030. 190 (Mar. 2007) 45-52.1010-603010.1016/j.jphotochem.2007.03.011www.sciencedirect.cominfo:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2023-07-21T12:14:32ZPortal AgregadorONG |
dc.title.none.fl_str_mv |
Synthesis of fluorescent tetracyclic lactams by a “one pot” three steps palladium-catalyzed borylation, Suzuki coupling (BSC) and lactamization. DNA and polynucleotides binding studies |
title |
Synthesis of fluorescent tetracyclic lactams by a “one pot” three steps palladium-catalyzed borylation, Suzuki coupling (BSC) and lactamization. DNA and polynucleotides binding studies |
spellingShingle |
Synthesis of fluorescent tetracyclic lactams by a “one pot” three steps palladium-catalyzed borylation, Suzuki coupling (BSC) and lactamization. DNA and polynucleotides binding studies Queiroz, Maria João R. P. Palladium-catalyzed BSC reaction Lactamization Benzothieno[2,3-c]quinolones Fluorescence DNA and polynucleotides binding palladiurn-catalyzed BSC reaction benzothieno[2,3-c]qumolones Science & Technology |
title_short |
Synthesis of fluorescent tetracyclic lactams by a “one pot” three steps palladium-catalyzed borylation, Suzuki coupling (BSC) and lactamization. DNA and polynucleotides binding studies |
title_full |
Synthesis of fluorescent tetracyclic lactams by a “one pot” three steps palladium-catalyzed borylation, Suzuki coupling (BSC) and lactamization. DNA and polynucleotides binding studies |
title_fullStr |
Synthesis of fluorescent tetracyclic lactams by a “one pot” three steps palladium-catalyzed borylation, Suzuki coupling (BSC) and lactamization. DNA and polynucleotides binding studies |
title_full_unstemmed |
Synthesis of fluorescent tetracyclic lactams by a “one pot” three steps palladium-catalyzed borylation, Suzuki coupling (BSC) and lactamization. DNA and polynucleotides binding studies |
title_sort |
Synthesis of fluorescent tetracyclic lactams by a “one pot” three steps palladium-catalyzed borylation, Suzuki coupling (BSC) and lactamization. DNA and polynucleotides binding studies |
author |
Queiroz, Maria João R. P. |
author_facet |
Queiroz, Maria João R. P. Castanheira, Elisabete M. S. Lopes, Teresa C. T. Cruz, Yvonne K. Kirsch, G. |
author_role |
author |
author2 |
Castanheira, Elisabete M. S. Lopes, Teresa C. T. Cruz, Yvonne K. Kirsch, G. |
author2_role |
author author author author |
dc.contributor.none.fl_str_mv |
Universidade do Minho |
dc.contributor.author.fl_str_mv |
Queiroz, Maria João R. P. Castanheira, Elisabete M. S. Lopes, Teresa C. T. Cruz, Yvonne K. Kirsch, G. |
dc.subject.por.fl_str_mv |
Palladium-catalyzed BSC reaction Lactamization Benzothieno[2,3-c]quinolones Fluorescence DNA and polynucleotides binding palladiurn-catalyzed BSC reaction benzothieno[2,3-c]qumolones Science & Technology |
topic |
Palladium-catalyzed BSC reaction Lactamization Benzothieno[2,3-c]quinolones Fluorescence DNA and polynucleotides binding palladiurn-catalyzed BSC reaction benzothieno[2,3-c]qumolones Science & Technology |
description |
Tetracyclic lactams (benzothieno[2,3-c]quinolones) were prepared by “one pot” three steps palladium-catalyzed borylation, Suzuki coupling (BSC) and lactamization, starting from ortho-haloanilines and alkyl 3-bromobenzo[b]thiophene-2-carboxylates. The former were used as the components to be borylated with pinacolborane, and the latter as the brominated component in the Suzuki coupling. The amidation occurred with loss of the alkyl alcohol, presumably in the Suzuki coupling product, giving the corresponding tetracyclic lactam. This constitutes a novel application of the BSC reaction using sterically hindered substrates. In this work studies of absorption and fluorescence in several solvents and in presence of salmon sperm DNA or synthetic double stranded (ds) heteropolynucleotides, poly(dA-dT)•(dA-dT) and poly(dG-dC)•(dG-dC), were performed. The binding constants values (Ki = 2.6x10^5- 4.5x10^5 M^-1) point to a high affinity of the lactams to DNA. It was shown that the intercalation is the prefered mode of binding and that the substituted new lactams (with F or OMe) exhibit a higher affinity for A-T regions. Quenching experiments with iodide show that the methoxylated lactam is the more intercalative in DNA. The same type of experiments using this compound bound to heteropolynucleotides show a very low accessibility (fa = 0.07) of the lactam in poly(dG-dC)•(dG-dC) to the quencher showing a large majority of intercalative binding while the high affinity for A-T regions together with a higher accessiblity (fa = 0.25) point to the possiblity of intercalative and groove binding. |
publishDate |
2007 |
dc.date.none.fl_str_mv |
2007-03 2007-03-01T00:00:00Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
https://hdl.handle.net/1822/8378 |
url |
https://hdl.handle.net/1822/8378 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
“Journal of Photochemistry and Photobiology A : Chemistry". ISSN 1010-6030. 190 (Mar. 2007) 45-52. 1010-6030 10.1016/j.jphotochem.2007.03.011 www.sciencedirect.com |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Elsevier |
publisher.none.fl_str_mv |
Elsevier |
dc.source.none.fl_str_mv |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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