Sigmatropic rearrangements in 5-allyloxytetrazoles
Autor(a) principal: | |
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Data de Publicação: | 2011 |
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/10400.1/4243 |
Resumo: | Mechanisms of thermal isomerization of allyl tetrazolyl ethers derived from the carbocyclic allylic alcohols cyclohex-2-enol and 3-methylcyclohex-2-enol and from the natural terpene alcohol nerol were investigated. In the process of the syntheses of the three 1-aryl-5-allyloxytetrazoles, their rapid isomerization to the corresponding 1-aryl-4-allyltetrazol-5-ones occurred. The experiments showed that the imidates rearrange exclusively through a [3,3¢]-sigmatropic migration of the allylic system from O to N, with inversion. Mechanistic proposals are based on product analysis and extensive quantum chemical calculations at the DFT(B3LYP) and MP2 levels, on O-allyl and N-allyl isomers and on putative transition state structures for [1,3¢]- and [3,3¢]-sigmatropic migrations. The experimental observations could be only explained on the basis of the MP2/6-31G(d,p) calculations that favoured the [3,3¢]-sigmatropic migrations, yielding lower energies both for the transition states and for the final isomerization products. |
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Sigmatropic rearrangements in 5-allyloxytetrazolesMechanisms of thermal isomerization of allyl tetrazolyl ethers derived from the carbocyclic allylic alcohols cyclohex-2-enol and 3-methylcyclohex-2-enol and from the natural terpene alcohol nerol were investigated. In the process of the syntheses of the three 1-aryl-5-allyloxytetrazoles, their rapid isomerization to the corresponding 1-aryl-4-allyltetrazol-5-ones occurred. The experiments showed that the imidates rearrange exclusively through a [3,3¢]-sigmatropic migration of the allylic system from O to N, with inversion. Mechanistic proposals are based on product analysis and extensive quantum chemical calculations at the DFT(B3LYP) and MP2 levels, on O-allyl and N-allyl isomers and on putative transition state structures for [1,3¢]- and [3,3¢]-sigmatropic migrations. The experimental observations could be only explained on the basis of the MP2/6-31G(d,p) calculations that favoured the [3,3¢]-sigmatropic migrations, yielding lower energies both for the transition states and for the final isomerization products.Royal Society of ChemistrySapientiaFrija, L.Reva, I. D.Ismael, AminCoelho, DanielaFausto, R.Cristiano, Maria Lurdes Santos2014-06-07T11:08:59Z20112014-06-05T09:01:02Z2011-01-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10400.1/4243engFrija, Luís M. T.; Reva, Igor; Ismael, Amin; Coelho, Daniela V.; Fausto, Rui; Cristiano, M. Lurdes S. Sigmatropic rearrangements in 5-allyloxytetrazoles, Organic & Biomolecular Chemistry, 9, 17, 6040-6054, 2011.1477-0520AUT: MCR00716http://dx.doi.org/10.1039/c1ob05460kinfo: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:RCAAP2023-07-24T10:15:30Zoai:sapientia.ualg.pt:10400.1/4243Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T19:57:41.478467Repositório 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 |
Sigmatropic rearrangements in 5-allyloxytetrazoles |
title |
Sigmatropic rearrangements in 5-allyloxytetrazoles |
spellingShingle |
Sigmatropic rearrangements in 5-allyloxytetrazoles Frija, L. |
title_short |
Sigmatropic rearrangements in 5-allyloxytetrazoles |
title_full |
Sigmatropic rearrangements in 5-allyloxytetrazoles |
title_fullStr |
Sigmatropic rearrangements in 5-allyloxytetrazoles |
title_full_unstemmed |
Sigmatropic rearrangements in 5-allyloxytetrazoles |
title_sort |
Sigmatropic rearrangements in 5-allyloxytetrazoles |
author |
Frija, L. |
author_facet |
Frija, L. Reva, I. D. Ismael, Amin Coelho, Daniela Fausto, R. Cristiano, Maria Lurdes Santos |
author_role |
author |
author2 |
Reva, I. D. Ismael, Amin Coelho, Daniela Fausto, R. Cristiano, Maria Lurdes Santos |
author2_role |
author author author author author |
dc.contributor.none.fl_str_mv |
Sapientia |
dc.contributor.author.fl_str_mv |
Frija, L. Reva, I. D. Ismael, Amin Coelho, Daniela Fausto, R. Cristiano, Maria Lurdes Santos |
description |
Mechanisms of thermal isomerization of allyl tetrazolyl ethers derived from the carbocyclic allylic alcohols cyclohex-2-enol and 3-methylcyclohex-2-enol and from the natural terpene alcohol nerol were investigated. In the process of the syntheses of the three 1-aryl-5-allyloxytetrazoles, their rapid isomerization to the corresponding 1-aryl-4-allyltetrazol-5-ones occurred. The experiments showed that the imidates rearrange exclusively through a [3,3¢]-sigmatropic migration of the allylic system from O to N, with inversion. Mechanistic proposals are based on product analysis and extensive quantum chemical calculations at the DFT(B3LYP) and MP2 levels, on O-allyl and N-allyl isomers and on putative transition state structures for [1,3¢]- and [3,3¢]-sigmatropic migrations. The experimental observations could be only explained on the basis of the MP2/6-31G(d,p) calculations that favoured the [3,3¢]-sigmatropic migrations, yielding lower energies both for the transition states and for the final isomerization products. |
publishDate |
2011 |
dc.date.none.fl_str_mv |
2011 2011-01-01T00:00:00Z 2014-06-07T11:08:59Z 2014-06-05T09:01:02Z |
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/10400.1/4243 |
url |
http://hdl.handle.net/10400.1/4243 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Frija, Luís M. T.; Reva, Igor; Ismael, Amin; Coelho, Daniela V.; Fausto, Rui; Cristiano, M. Lurdes S. Sigmatropic rearrangements in 5-allyloxytetrazoles, Organic & Biomolecular Chemistry, 9, 17, 6040-6054, 2011. 1477-0520 AUT: MCR00716 http://dx.doi.org/10.1039/c1ob05460k |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
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application/pdf |
dc.publisher.none.fl_str_mv |
Royal Society of Chemistry |
publisher.none.fl_str_mv |
Royal Society of Chemistry |
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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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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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