Absolute Configuration of (−)-Cubebin, a Classical Lignan with Pharmacological Potential, Defined by Means of Chiroptical Spectroscopy
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=S0103-50532020001002030 |
Resumo: | This work describes the first determination of the absolute configuration (AC) of (−)-cubebin by means of electronic circular dichroism (ECD), supported by quantum chemical calculations. The comparison of experimental ECD with the corresponding quantum chemical prediction for the proper diastereoisomer resulted in the definitive assignment of the AC of the naturally occurring (−)-cubebin as (8R,8aR,9S). The challenging determination of the relative configuration (RC) of cubebin based only on experimental nuclear magnetic resonance (NMR) methods is stressed. Computation of the 13C and 1H NMR chemical shifts for all the possible diastereoisomers leads to values of mean absolute error and root mean square deviation that do not allow distinguishing among them. Thus, errors in stereochemical determination can easily occur even when using two-dimensional methods, which clearly demonstrate the complexity of this special case. To determine the RC of this bioactive natural compound with high level of confidence, it was necessary to combine the DP4+ method with X-ray crystallography. Therefore, employing the commonly used empirical methods to determine the AC of (−)-cubebin can easily lead to misassignment of its stereochemistry. |
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Absolute Configuration of (−)-Cubebin, a Classical Lignan with Pharmacological Potential, Defined by Means of Chiroptical Spectroscopycubebinabsolute configurationNMR simulationX-ray crystallographyECDThis work describes the first determination of the absolute configuration (AC) of (−)-cubebin by means of electronic circular dichroism (ECD), supported by quantum chemical calculations. The comparison of experimental ECD with the corresponding quantum chemical prediction for the proper diastereoisomer resulted in the definitive assignment of the AC of the naturally occurring (−)-cubebin as (8R,8aR,9S). The challenging determination of the relative configuration (RC) of cubebin based only on experimental nuclear magnetic resonance (NMR) methods is stressed. Computation of the 13C and 1H NMR chemical shifts for all the possible diastereoisomers leads to values of mean absolute error and root mean square deviation that do not allow distinguishing among them. Thus, errors in stereochemical determination can easily occur even when using two-dimensional methods, which clearly demonstrate the complexity of this special case. To determine the RC of this bioactive natural compound with high level of confidence, it was necessary to combine the DP4+ method with X-ray crystallography. Therefore, employing the commonly used empirical methods to determine the AC of (−)-cubebin can easily lead to misassignment of its stereochemistry.Sociedade Brasileira de Química2020-10-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532020001002030Journal of the Brazilian Chemical Society v.31 n.10 2020reponame:Journal of the Brazilian Chemical Society (Online)instname:Sociedade Brasileira de Química (SBQ)instacron:SBQ10.21577/0103-5053.20200103info:eu-repo/semantics/openAccessMacedo,Arthur L.Martorano,Lucas H.Albuquerque,Ana Carolina F. deFiorot,Rodolfo G.Carneiro,José W. M.Campos,Vinicius R.Vasconcelos,Thatyana R. A.Valverde,Alessandra L.Moreira,Davyson L.Santos Jr.,Fernando M. doseng2020-10-07T00:00:00Zoai:scielo:S0103-50532020001002030Revistahttp://jbcs.sbq.org.brONGhttps://old.scielo.br/oai/scielo-oai.php||office@jbcs.sbq.org.br1678-47900103-5053opendoar:2020-10-07T00:00Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ)false |
dc.title.none.fl_str_mv |
Absolute Configuration of (−)-Cubebin, a Classical Lignan with Pharmacological Potential, Defined by Means of Chiroptical Spectroscopy |
title |
Absolute Configuration of (−)-Cubebin, a Classical Lignan with Pharmacological Potential, Defined by Means of Chiroptical Spectroscopy |
spellingShingle |
Absolute Configuration of (−)-Cubebin, a Classical Lignan with Pharmacological Potential, Defined by Means of Chiroptical Spectroscopy Macedo,Arthur L. cubebin absolute configuration NMR simulation X-ray crystallography ECD |
title_short |
Absolute Configuration of (−)-Cubebin, a Classical Lignan with Pharmacological Potential, Defined by Means of Chiroptical Spectroscopy |
title_full |
Absolute Configuration of (−)-Cubebin, a Classical Lignan with Pharmacological Potential, Defined by Means of Chiroptical Spectroscopy |
title_fullStr |
Absolute Configuration of (−)-Cubebin, a Classical Lignan with Pharmacological Potential, Defined by Means of Chiroptical Spectroscopy |
title_full_unstemmed |
Absolute Configuration of (−)-Cubebin, a Classical Lignan with Pharmacological Potential, Defined by Means of Chiroptical Spectroscopy |
title_sort |
Absolute Configuration of (−)-Cubebin, a Classical Lignan with Pharmacological Potential, Defined by Means of Chiroptical Spectroscopy |
author |
Macedo,Arthur L. |
author_facet |
Macedo,Arthur L. Martorano,Lucas H. Albuquerque,Ana Carolina F. de Fiorot,Rodolfo G. Carneiro,José W. M. Campos,Vinicius R. Vasconcelos,Thatyana R. A. Valverde,Alessandra L. Moreira,Davyson L. Santos Jr.,Fernando M. dos |
author_role |
author |
author2 |
Martorano,Lucas H. Albuquerque,Ana Carolina F. de Fiorot,Rodolfo G. Carneiro,José W. M. Campos,Vinicius R. Vasconcelos,Thatyana R. A. Valverde,Alessandra L. Moreira,Davyson L. Santos Jr.,Fernando M. dos |
author2_role |
author author author author author author author author author |
dc.contributor.author.fl_str_mv |
Macedo,Arthur L. Martorano,Lucas H. Albuquerque,Ana Carolina F. de Fiorot,Rodolfo G. Carneiro,José W. M. Campos,Vinicius R. Vasconcelos,Thatyana R. A. Valverde,Alessandra L. Moreira,Davyson L. Santos Jr.,Fernando M. dos |
dc.subject.por.fl_str_mv |
cubebin absolute configuration NMR simulation X-ray crystallography ECD |
topic |
cubebin absolute configuration NMR simulation X-ray crystallography ECD |
description |
This work describes the first determination of the absolute configuration (AC) of (−)-cubebin by means of electronic circular dichroism (ECD), supported by quantum chemical calculations. The comparison of experimental ECD with the corresponding quantum chemical prediction for the proper diastereoisomer resulted in the definitive assignment of the AC of the naturally occurring (−)-cubebin as (8R,8aR,9S). The challenging determination of the relative configuration (RC) of cubebin based only on experimental nuclear magnetic resonance (NMR) methods is stressed. Computation of the 13C and 1H NMR chemical shifts for all the possible diastereoisomers leads to values of mean absolute error and root mean square deviation that do not allow distinguishing among them. Thus, errors in stereochemical determination can easily occur even when using two-dimensional methods, which clearly demonstrate the complexity of this special case. To determine the RC of this bioactive natural compound with high level of confidence, it was necessary to combine the DP4+ method with X-ray crystallography. Therefore, employing the commonly used empirical methods to determine the AC of (−)-cubebin can easily lead to misassignment of its stereochemistry. |
publishDate |
2020 |
dc.date.none.fl_str_mv |
2020-10-01 |
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=S0103-50532020001002030 |
url |
http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532020001002030 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
10.21577/0103-5053.20200103 |
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.10 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 |
_version_ |
1750318183461421056 |