Study based on electronic descriptors of the diastereoselective aza-diels-alder cycloaddition of [(1r)-10-(n,n-diethylsulfamoyl)isobornyl] 2h-azirine-3-carboxylate to e,e-1,4-diacetoxy-1,3-butadiene
Autor(a) principal: | |
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Data de Publicação: | 2013 |
Outros Autores: | , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/1822/63863 |
Resumo: | Cycloaddition of chiral [(1R)-10-(N,N-diethylsulfamoyl)isobornyl] 2H-azirine-3-carboxylate to E,E-1,4-diacetoxy-1,3-butadiene shows complete diatereoselectivity giving a single cycloadduct (-)-(2S,5R,6R)-6-[(1R)-10-(N,N-diethylsulfamoyl)isobornyloxycarbonyl]-1-azabicyclo[4.1.0]hept-3-ene-2,5-diyldiacetate. Our main objective is to identify electronic/steric parameters capable of describing the observed tendencies of this reaction. The results of the calculations conclude that: even though the steric factors can play an important role at the initial steps of the reaction, at the transition states the behavior of several electronic parameters; like hardness, polarizability, aromaticity, charge transfer, etc is decisive enough to justify the obtained product. Finally, this work summarizes an exhaustive analysis of electronic descriptors and empirical reactivity principles, reaching a definitive and comprehensive explanation to the observed experimental result. |
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Study based on electronic descriptors of the diastereoselective aza-diels-alder cycloaddition of [(1r)-10-(n,n-diethylsulfamoyl)isobornyl] 2h-azirine-3-carboxylate to e,e-1,4-diacetoxy-1,3-butadieneMaximum hardness principleMinimum polarizability principlereactvity principlesaromaticity of transition states2H-azirine-3-carboxylateCiências Naturais::Ciências QuímicasScience & TechnologyCycloaddition of chiral [(1R)-10-(N,N-diethylsulfamoyl)isobornyl] 2H-azirine-3-carboxylate to E,E-1,4-diacetoxy-1,3-butadiene shows complete diatereoselectivity giving a single cycloadduct (-)-(2S,5R,6R)-6-[(1R)-10-(N,N-diethylsulfamoyl)isobornyloxycarbonyl]-1-azabicyclo[4.1.0]hept-3-ene-2,5-diyldiacetate. Our main objective is to identify electronic/steric parameters capable of describing the observed tendencies of this reaction. The results of the calculations conclude that: even though the steric factors can play an important role at the initial steps of the reaction, at the transition states the behavior of several electronic parameters; like hardness, polarizability, aromaticity, charge transfer, etc is decisive enough to justify the obtained product. Finally, this work summarizes an exhaustive analysis of electronic descriptors and empirical reactivity principles, reaching a definitive and comprehensive explanation to the observed experimental result.Thanks to Fundação para a Ciência e Tecnologia (FCT) for partial financial support (project PTDC/QUI/67407/2006)Sociedad Chilena de QuimicaUniversidade do MinhoRuiz-Blanco, Yasser B.Alves, Maria José ChãoRodríguez-Borges, José E.Molina, Reinaldo20132013-01-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/1822/63863eng0717-93240717-970710.4067/S0717-97072013000400074https://scielo.conicyt.cl/scielo.php?script=sci_arttext&pid=S0717-97072013000400074&lng=en&nrm=iso&tlng=eninfo: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:RCAAP2023-07-21T12:27:35Zoai:repositorium.sdum.uminho.pt:1822/63863Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T19:22:13.547688Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Study based on electronic descriptors of the diastereoselective aza-diels-alder cycloaddition of [(1r)-10-(n,n-diethylsulfamoyl)isobornyl] 2h-azirine-3-carboxylate to e,e-1,4-diacetoxy-1,3-butadiene |
title |
Study based on electronic descriptors of the diastereoselective aza-diels-alder cycloaddition of [(1r)-10-(n,n-diethylsulfamoyl)isobornyl] 2h-azirine-3-carboxylate to e,e-1,4-diacetoxy-1,3-butadiene |
spellingShingle |
Study based on electronic descriptors of the diastereoselective aza-diels-alder cycloaddition of [(1r)-10-(n,n-diethylsulfamoyl)isobornyl] 2h-azirine-3-carboxylate to e,e-1,4-diacetoxy-1,3-butadiene Ruiz-Blanco, Yasser B. Maximum hardness principle Minimum polarizability principle reactvity principles aromaticity of transition states 2H-azirine-3-carboxylate Ciências Naturais::Ciências Químicas Science & Technology |
title_short |
Study based on electronic descriptors of the diastereoselective aza-diels-alder cycloaddition of [(1r)-10-(n,n-diethylsulfamoyl)isobornyl] 2h-azirine-3-carboxylate to e,e-1,4-diacetoxy-1,3-butadiene |
title_full |
Study based on electronic descriptors of the diastereoselective aza-diels-alder cycloaddition of [(1r)-10-(n,n-diethylsulfamoyl)isobornyl] 2h-azirine-3-carboxylate to e,e-1,4-diacetoxy-1,3-butadiene |
title_fullStr |
Study based on electronic descriptors of the diastereoselective aza-diels-alder cycloaddition of [(1r)-10-(n,n-diethylsulfamoyl)isobornyl] 2h-azirine-3-carboxylate to e,e-1,4-diacetoxy-1,3-butadiene |
title_full_unstemmed |
Study based on electronic descriptors of the diastereoselective aza-diels-alder cycloaddition of [(1r)-10-(n,n-diethylsulfamoyl)isobornyl] 2h-azirine-3-carboxylate to e,e-1,4-diacetoxy-1,3-butadiene |
title_sort |
Study based on electronic descriptors of the diastereoselective aza-diels-alder cycloaddition of [(1r)-10-(n,n-diethylsulfamoyl)isobornyl] 2h-azirine-3-carboxylate to e,e-1,4-diacetoxy-1,3-butadiene |
author |
Ruiz-Blanco, Yasser B. |
author_facet |
Ruiz-Blanco, Yasser B. Alves, Maria José Chão Rodríguez-Borges, José E. Molina, Reinaldo |
author_role |
author |
author2 |
Alves, Maria José Chão Rodríguez-Borges, José E. Molina, Reinaldo |
author2_role |
author author author |
dc.contributor.none.fl_str_mv |
Universidade do Minho |
dc.contributor.author.fl_str_mv |
Ruiz-Blanco, Yasser B. Alves, Maria José Chão Rodríguez-Borges, José E. Molina, Reinaldo |
dc.subject.por.fl_str_mv |
Maximum hardness principle Minimum polarizability principle reactvity principles aromaticity of transition states 2H-azirine-3-carboxylate Ciências Naturais::Ciências Químicas Science & Technology |
topic |
Maximum hardness principle Minimum polarizability principle reactvity principles aromaticity of transition states 2H-azirine-3-carboxylate Ciências Naturais::Ciências Químicas Science & Technology |
description |
Cycloaddition of chiral [(1R)-10-(N,N-diethylsulfamoyl)isobornyl] 2H-azirine-3-carboxylate to E,E-1,4-diacetoxy-1,3-butadiene shows complete diatereoselectivity giving a single cycloadduct (-)-(2S,5R,6R)-6-[(1R)-10-(N,N-diethylsulfamoyl)isobornyloxycarbonyl]-1-azabicyclo[4.1.0]hept-3-ene-2,5-diyldiacetate. Our main objective is to identify electronic/steric parameters capable of describing the observed tendencies of this reaction. The results of the calculations conclude that: even though the steric factors can play an important role at the initial steps of the reaction, at the transition states the behavior of several electronic parameters; like hardness, polarizability, aromaticity, charge transfer, etc is decisive enough to justify the obtained product. Finally, this work summarizes an exhaustive analysis of electronic descriptors and empirical reactivity principles, reaching a definitive and comprehensive explanation to the observed experimental result. |
publishDate |
2013 |
dc.date.none.fl_str_mv |
2013 2013-01-01T00:00:00Z |
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 |
http://hdl.handle.net/1822/63863 |
url |
http://hdl.handle.net/1822/63863 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
0717-9324 0717-9707 10.4067/S0717-97072013000400074 https://scielo.conicyt.cl/scielo.php?script=sci_arttext&pid=S0717-97072013000400074&lng=en&nrm=iso&tlng=en |
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 |
Sociedad Chilena de Quimica |
publisher.none.fl_str_mv |
Sociedad Chilena de Quimica |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
instacron_str |
RCAAP |
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RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository.name.fl_str_mv |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
repository.mail.fl_str_mv |
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1799132692363608064 |