Quantum mechanical approach for structure elucidation of novel halogenated sesquiterpene lactones
Autor(a) principal: | |
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Data de Publicação: | 2019 |
Outros Autores: | , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | LOCUS Repositório Institucional da UFV |
Texto Completo: | https://doi.org/10.1016/j.molstruc.2018.11.085 http://www.locus.ufv.br/handle/123456789/23852 |
Resumo: | The stereochemistries of halogenated lumisantonin were rationalized by four distinct methods. In the first method the activation energies for the halonium ion intermediates and the reaction energies for all candidate structures were calculated. In the second approach the coupling constants were calculated and compared with the experimental values. The best matches for the calculated and experimental coupling constants were achieved by the modified procedure. In the third approach the computed 1H and 13C NMR chemical shifts were compared with the experimental values and the mean absolute errors (MAE) were measured. In the fourth method the adapted DP4 probabilities were evaluated and the determined stereochemistries for the sesquiterpene lactones (3a and 4a) were in agreement with the first three protocols. |
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Alvarenga, Elson S.Santos, Juliana O.Moraes, Fernanda C.Carneiro, Vânia M. T.2019-03-11T17:06:36Z2019-03-11T17:06:36Z2019-03-150167-7322https://doi.org/10.1016/j.molstruc.2018.11.085http://www.locus.ufv.br/handle/123456789/23852The stereochemistries of halogenated lumisantonin were rationalized by four distinct methods. In the first method the activation energies for the halonium ion intermediates and the reaction energies for all candidate structures were calculated. In the second approach the coupling constants were calculated and compared with the experimental values. The best matches for the calculated and experimental coupling constants were achieved by the modified procedure. In the third approach the computed 1H and 13C NMR chemical shifts were compared with the experimental values and the mean absolute errors (MAE) were measured. In the fourth method the adapted DP4 probabilities were evaluated and the determined stereochemistries for the sesquiterpene lactones (3a and 4a) were in agreement with the first three protocols.engJournal of Molecular StructureVolume 1180, 15 March 2019, Pages 41-47Elsevier B. V.info:eu-repo/semantics/openAccessGIAOLumisantoninHalogenationMAEDP4Coupling constantQuantum mechanical approach for structure elucidation of novel halogenated sesquiterpene lactonesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfreponame:LOCUS Repositório Institucional da UFVinstname:Universidade Federal de Viçosa (UFV)instacron:UFVORIGINALartigo.pdfartigo.pdfTexto completoapplication/pdf457237https://locus.ufv.br//bitstream/123456789/23852/1/artigo.pdf2b31ae11f776ebc21bd0e510e7935653MD51LICENSElicense.txtlicense.txttext/plain; charset=utf-81748https://locus.ufv.br//bitstream/123456789/23852/2/license.txt8a4605be74aa9ea9d79846c1fba20a33MD52123456789/238522019-03-11 14:08:34.933oai:locus.ufv.br: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Repositório InstitucionalPUBhttps://www.locus.ufv.br/oai/requestfabiojreis@ufv.bropendoar:21452019-03-11T17:08:34LOCUS Repositório Institucional da UFV - Universidade Federal de Viçosa (UFV)false |
dc.title.en.fl_str_mv |
Quantum mechanical approach for structure elucidation of novel halogenated sesquiterpene lactones |
title |
Quantum mechanical approach for structure elucidation of novel halogenated sesquiterpene lactones |
spellingShingle |
Quantum mechanical approach for structure elucidation of novel halogenated sesquiterpene lactones Alvarenga, Elson S. GIAO Lumisantonin Halogenation MAEDP4 Coupling constant |
title_short |
Quantum mechanical approach for structure elucidation of novel halogenated sesquiterpene lactones |
title_full |
Quantum mechanical approach for structure elucidation of novel halogenated sesquiterpene lactones |
title_fullStr |
Quantum mechanical approach for structure elucidation of novel halogenated sesquiterpene lactones |
title_full_unstemmed |
Quantum mechanical approach for structure elucidation of novel halogenated sesquiterpene lactones |
title_sort |
Quantum mechanical approach for structure elucidation of novel halogenated sesquiterpene lactones |
author |
Alvarenga, Elson S. |
author_facet |
Alvarenga, Elson S. Santos, Juliana O. Moraes, Fernanda C. Carneiro, Vânia M. T. |
author_role |
author |
author2 |
Santos, Juliana O. Moraes, Fernanda C. Carneiro, Vânia M. T. |
author2_role |
author author author |
dc.contributor.author.fl_str_mv |
Alvarenga, Elson S. Santos, Juliana O. Moraes, Fernanda C. Carneiro, Vânia M. T. |
dc.subject.pt-BR.fl_str_mv |
GIAO Lumisantonin Halogenation MAEDP4 Coupling constant |
topic |
GIAO Lumisantonin Halogenation MAEDP4 Coupling constant |
description |
The stereochemistries of halogenated lumisantonin were rationalized by four distinct methods. In the first method the activation energies for the halonium ion intermediates and the reaction energies for all candidate structures were calculated. In the second approach the coupling constants were calculated and compared with the experimental values. The best matches for the calculated and experimental coupling constants were achieved by the modified procedure. In the third approach the computed 1H and 13C NMR chemical shifts were compared with the experimental values and the mean absolute errors (MAE) were measured. In the fourth method the adapted DP4 probabilities were evaluated and the determined stereochemistries for the sesquiterpene lactones (3a and 4a) were in agreement with the first three protocols. |
publishDate |
2019 |
dc.date.accessioned.fl_str_mv |
2019-03-11T17:06:36Z |
dc.date.available.fl_str_mv |
2019-03-11T17:06:36Z |
dc.date.issued.fl_str_mv |
2019-03-15 |
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://doi.org/10.1016/j.molstruc.2018.11.085 http://www.locus.ufv.br/handle/123456789/23852 |
dc.identifier.issn.none.fl_str_mv |
0167-7322 |
identifier_str_mv |
0167-7322 |
url |
https://doi.org/10.1016/j.molstruc.2018.11.085 http://www.locus.ufv.br/handle/123456789/23852 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.ispartofseries.pt-BR.fl_str_mv |
Volume 1180, 15 March 2019, Pages 41-47 |
dc.rights.driver.fl_str_mv |
Elsevier B. V. info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Elsevier B. V. |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Journal of Molecular Structure |
publisher.none.fl_str_mv |
Journal of Molecular Structure |
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LOCUS Repositório Institucional da UFV |
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