Acid-Catalyzed Z-E Isomerization of γ-Alkylidenebutenolides: An Experimental and DFT Study
Autor(a) principal: | |
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Data de Publicação: | 2020 |
Outros Autores: | , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Journal of the Brazilian Chemical Society (Online) |
Texto Completo: | http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532020000100090 |
Resumo: | The Z-E isomerization of γ-alkylidenebutenolide analogues to natural nostoclides and other natural butenolides was investigated using 1H nuclear magnetic resonance (NMR) and high performance liquid chromatography (HPLC) data as well as density functional theory (DFT) calculations at the wB97x-D/6-31G(d,p) level, including solvent effects with the polarizable continuum solvation approach. The experimental data supported the Z to E isomerization of γ-alkylidenebutenolides under acid catalysis. Newly prepared samples have predominantly Z configuration, which partially isomerizes to the E isomer under acidic conditions. Density functional theory studies corroborate the experimental findings. While neutral γ-alkylidenebutenolides are more stable in the Z form, protonation of the γ-lactone carbonyl group results in preferential stabilization of the E isomer. |
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Acid-Catalyzed Z-E Isomerization of γ-Alkylidenebutenolides: An Experimental and DFT StudynostoclideZ-E isomerizationbutenolidesγ-lactoneDFT calculationsacid catalysisThe Z-E isomerization of γ-alkylidenebutenolide analogues to natural nostoclides and other natural butenolides was investigated using 1H nuclear magnetic resonance (NMR) and high performance liquid chromatography (HPLC) data as well as density functional theory (DFT) calculations at the wB97x-D/6-31G(d,p) level, including solvent effects with the polarizable continuum solvation approach. The experimental data supported the Z to E isomerization of γ-alkylidenebutenolides under acid catalysis. Newly prepared samples have predominantly Z configuration, which partially isomerizes to the E isomer under acidic conditions. Density functional theory studies corroborate the experimental findings. While neutral γ-alkylidenebutenolides are more stable in the Z form, protonation of the γ-lactone carbonyl group results in preferential stabilization of the E isomer.Sociedade Brasileira de Química2020-01-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532020000100090Journal of the Brazilian Chemical Society v.31 n.1 2020reponame:Journal of the Brazilian Chemical Society (Online)instname:Sociedade Brasileira de Química (SBQ)instacron:SBQ10.21577/0103-5053.20190131info:eu-repo/semantics/openAccessVarejão,Jodieh O. S.Barbosa,Luiz C. A.Varejão,Eduardo V. V.Souza,Aline H.Lage,Mateus R.Carneiro,José W. M.eng2020-06-05T00:00:00Zoai:scielo:S0103-50532020000100090Revistahttp://jbcs.sbq.org.brONGhttps://old.scielo.br/oai/scielo-oai.php||office@jbcs.sbq.org.br1678-47900103-5053opendoar:2020-06-05T00:00Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ)false |
dc.title.none.fl_str_mv |
Acid-Catalyzed Z-E Isomerization of γ-Alkylidenebutenolides: An Experimental and DFT Study |
title |
Acid-Catalyzed Z-E Isomerization of γ-Alkylidenebutenolides: An Experimental and DFT Study |
spellingShingle |
Acid-Catalyzed Z-E Isomerization of γ-Alkylidenebutenolides: An Experimental and DFT Study Varejão,Jodieh O. S. nostoclide Z-E isomerization butenolides γ-lactone DFT calculations acid catalysis |
title_short |
Acid-Catalyzed Z-E Isomerization of γ-Alkylidenebutenolides: An Experimental and DFT Study |
title_full |
Acid-Catalyzed Z-E Isomerization of γ-Alkylidenebutenolides: An Experimental and DFT Study |
title_fullStr |
Acid-Catalyzed Z-E Isomerization of γ-Alkylidenebutenolides: An Experimental and DFT Study |
title_full_unstemmed |
Acid-Catalyzed Z-E Isomerization of γ-Alkylidenebutenolides: An Experimental and DFT Study |
title_sort |
Acid-Catalyzed Z-E Isomerization of γ-Alkylidenebutenolides: An Experimental and DFT Study |
author |
Varejão,Jodieh O. S. |
author_facet |
Varejão,Jodieh O. S. Barbosa,Luiz C. A. Varejão,Eduardo V. V. Souza,Aline H. Lage,Mateus R. Carneiro,José W. M. |
author_role |
author |
author2 |
Barbosa,Luiz C. A. Varejão,Eduardo V. V. Souza,Aline H. Lage,Mateus R. Carneiro,José W. M. |
author2_role |
author author author author author |
dc.contributor.author.fl_str_mv |
Varejão,Jodieh O. S. Barbosa,Luiz C. A. Varejão,Eduardo V. V. Souza,Aline H. Lage,Mateus R. Carneiro,José W. M. |
dc.subject.por.fl_str_mv |
nostoclide Z-E isomerization butenolides γ-lactone DFT calculations acid catalysis |
topic |
nostoclide Z-E isomerization butenolides γ-lactone DFT calculations acid catalysis |
description |
The Z-E isomerization of γ-alkylidenebutenolide analogues to natural nostoclides and other natural butenolides was investigated using 1H nuclear magnetic resonance (NMR) and high performance liquid chromatography (HPLC) data as well as density functional theory (DFT) calculations at the wB97x-D/6-31G(d,p) level, including solvent effects with the polarizable continuum solvation approach. The experimental data supported the Z to E isomerization of γ-alkylidenebutenolides under acid catalysis. Newly prepared samples have predominantly Z configuration, which partially isomerizes to the E isomer under acidic conditions. Density functional theory studies corroborate the experimental findings. While neutral γ-alkylidenebutenolides are more stable in the Z form, protonation of the γ-lactone carbonyl group results in preferential stabilization of the E isomer. |
publishDate |
2020 |
dc.date.none.fl_str_mv |
2020-01-01 |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532020000100090 |
url |
http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532020000100090 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
10.21577/0103-5053.20190131 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
text/html |
dc.publisher.none.fl_str_mv |
Sociedade Brasileira de Química |
publisher.none.fl_str_mv |
Sociedade Brasileira de Química |
dc.source.none.fl_str_mv |
Journal of the Brazilian Chemical Society v.31 n.1 2020 reponame:Journal of the Brazilian Chemical Society (Online) instname:Sociedade Brasileira de Química (SBQ) instacron:SBQ |
instname_str |
Sociedade Brasileira de Química (SBQ) |
instacron_str |
SBQ |
institution |
SBQ |
reponame_str |
Journal of the Brazilian Chemical Society (Online) |
collection |
Journal of the Brazilian Chemical Society (Online) |
repository.name.fl_str_mv |
Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ) |
repository.mail.fl_str_mv |
||office@jbcs.sbq.org.br |
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1750318182541819904 |