Diels–alder reactions of alkyl 2H-azirine-3-carboxylates with furans
Autor(a) principal: | |
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Data de Publicação: | 2001 |
Outros Autores: | , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | https://hdl.handle.net/1822/2181 |
Resumo: | Methyl 2-(2,6-dichlorophenyl)-2H-azirine-3-carboxylate 1 and furan give the aziridine 2 by a Diels–Alder cycloaddition reaction. The hydrolysis of compound 2 leads to a dihydrofuranol 11 by cleavage of a C–N bond. X-Ray crystal structures of compounds 2 and 11 have been determined. Compound 2 reacts with alcohols in a similar way to give 2-alkoxy-2,5-dihydrofurans as mixtures of cis and trans isomers. The structures of these compounds have been determined from an X-ray crystal structure of one of the methyl ethers, the trans isomer 13. The reaction of the azirine 1 with 1,3-diphenylisobenzofuran leads to the formation of two isomeric 1 : 1 adducts that have been identified as the products of endo and exo cycloaddition, 3 and 4. The endo isomer 3 is converted into the exo isomer 4 by heat. Similar Diels–Alder reactions have been carried out between furans and benzyl 2H-azirine-3-carboxylate 6. Hydrolysis of the adduct 7 formed with furan again produces a dihydrofuranol 25 as the major product together with three minor products, two of which are 1-azabicyclo[4.1.0]hept-3-ene-2,5-diols 27 and 28 that result from C–O bond cleavage. Protection of the mixture of alcohols with TBS triflate gives the bis(TBS) ether 31 of the trans-1-azabicyclo[4.1.0]hept-3-ene-2,5-diol as the major product, showing that this ring system can be produced from the dihydrofuranol 25. The bis(TBS) ether 30 of the cis-2,5-diol is a minor product and its structure has been established by independent synthesis through a Diels–Alder reaction between the azirine 6 and 1,4-bis(tert-butyldimethylsilyloxy)butadiene 32. |
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Diels–alder reactions of alkyl 2H-azirine-3-carboxylates with furansDiels-alder2H-azirinesScience & TechnologyMethyl 2-(2,6-dichlorophenyl)-2H-azirine-3-carboxylate 1 and furan give the aziridine 2 by a Diels–Alder cycloaddition reaction. The hydrolysis of compound 2 leads to a dihydrofuranol 11 by cleavage of a C–N bond. X-Ray crystal structures of compounds 2 and 11 have been determined. Compound 2 reacts with alcohols in a similar way to give 2-alkoxy-2,5-dihydrofurans as mixtures of cis and trans isomers. The structures of these compounds have been determined from an X-ray crystal structure of one of the methyl ethers, the trans isomer 13. The reaction of the azirine 1 with 1,3-diphenylisobenzofuran leads to the formation of two isomeric 1 : 1 adducts that have been identified as the products of endo and exo cycloaddition, 3 and 4. The endo isomer 3 is converted into the exo isomer 4 by heat. Similar Diels–Alder reactions have been carried out between furans and benzyl 2H-azirine-3-carboxylate 6. Hydrolysis of the adduct 7 formed with furan again produces a dihydrofuranol 25 as the major product together with three minor products, two of which are 1-azabicyclo[4.1.0]hept-3-ene-2,5-diols 27 and 28 that result from C–O bond cleavage. Protection of the mixture of alcohols with TBS triflate gives the bis(TBS) ether 31 of the trans-1-azabicyclo[4.1.0]hept-3-ene-2,5-diol as the major product, showing that this ring system can be produced from the dihydrofuranol 25. The bis(TBS) ether 30 of the cis-2,5-diol is a minor product and its structure has been established by independent synthesis through a Diels–Alder reaction between the azirine 6 and 1,4-bis(tert-butyldimethylsilyloxy)butadiene 32.Fundação para a Ciência e Tecnologia - POCTI/32723/QUI/2000. FEDER. EPSRC.Royal Society of ChemistryUniversidade do MinhoAlves, M. JoséAzóia, Nuno G.Bickley, Jamie F.Fortes, A. GilGilchrist, Thomas L.Mendonça, Ricardo20012001-01-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/1822/2181engAlves, M. J., Azoia, N. G., Bickley, J. F., Fortes, A. G., Gilchrist, T. L., & Mendonça, R. (2001). Diels–Alder reactions of alkyl 2H-azirine-3-carboxylates with furans. Journal of the Chemical Society, Perkin Transactions 1. Royal Society of Chemistry (RSC). http://doi.org/10.1039/b106985n1472-778110.1039/b106985ninfo: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:RCAAP2023-07-21T12:51:56Zoai:repositorium.sdum.uminho.pt:1822/2181Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T19:50:57.213709Repositório 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 |
Diels–alder reactions of alkyl 2H-azirine-3-carboxylates with furans |
title |
Diels–alder reactions of alkyl 2H-azirine-3-carboxylates with furans |
spellingShingle |
Diels–alder reactions of alkyl 2H-azirine-3-carboxylates with furans Alves, M. José Diels-alder 2H-azirines Science & Technology |
title_short |
Diels–alder reactions of alkyl 2H-azirine-3-carboxylates with furans |
title_full |
Diels–alder reactions of alkyl 2H-azirine-3-carboxylates with furans |
title_fullStr |
Diels–alder reactions of alkyl 2H-azirine-3-carboxylates with furans |
title_full_unstemmed |
Diels–alder reactions of alkyl 2H-azirine-3-carboxylates with furans |
title_sort |
Diels–alder reactions of alkyl 2H-azirine-3-carboxylates with furans |
author |
Alves, M. José |
author_facet |
Alves, M. José Azóia, Nuno G. Bickley, Jamie F. Fortes, A. Gil Gilchrist, Thomas L. Mendonça, Ricardo |
author_role |
author |
author2 |
Azóia, Nuno G. Bickley, Jamie F. Fortes, A. Gil Gilchrist, Thomas L. Mendonça, Ricardo |
author2_role |
author author author author author |
dc.contributor.none.fl_str_mv |
Universidade do Minho |
dc.contributor.author.fl_str_mv |
Alves, M. José Azóia, Nuno G. Bickley, Jamie F. Fortes, A. Gil Gilchrist, Thomas L. Mendonça, Ricardo |
dc.subject.por.fl_str_mv |
Diels-alder 2H-azirines Science & Technology |
topic |
Diels-alder 2H-azirines Science & Technology |
description |
Methyl 2-(2,6-dichlorophenyl)-2H-azirine-3-carboxylate 1 and furan give the aziridine 2 by a Diels–Alder cycloaddition reaction. The hydrolysis of compound 2 leads to a dihydrofuranol 11 by cleavage of a C–N bond. X-Ray crystal structures of compounds 2 and 11 have been determined. Compound 2 reacts with alcohols in a similar way to give 2-alkoxy-2,5-dihydrofurans as mixtures of cis and trans isomers. The structures of these compounds have been determined from an X-ray crystal structure of one of the methyl ethers, the trans isomer 13. The reaction of the azirine 1 with 1,3-diphenylisobenzofuran leads to the formation of two isomeric 1 : 1 adducts that have been identified as the products of endo and exo cycloaddition, 3 and 4. The endo isomer 3 is converted into the exo isomer 4 by heat. Similar Diels–Alder reactions have been carried out between furans and benzyl 2H-azirine-3-carboxylate 6. Hydrolysis of the adduct 7 formed with furan again produces a dihydrofuranol 25 as the major product together with three minor products, two of which are 1-azabicyclo[4.1.0]hept-3-ene-2,5-diols 27 and 28 that result from C–O bond cleavage. Protection of the mixture of alcohols with TBS triflate gives the bis(TBS) ether 31 of the trans-1-azabicyclo[4.1.0]hept-3-ene-2,5-diol as the major product, showing that this ring system can be produced from the dihydrofuranol 25. The bis(TBS) ether 30 of the cis-2,5-diol is a minor product and its structure has been established by independent synthesis through a Diels–Alder reaction between the azirine 6 and 1,4-bis(tert-butyldimethylsilyloxy)butadiene 32. |
publishDate |
2001 |
dc.date.none.fl_str_mv |
2001 2001-01-01T00:00:00Z |
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 |
https://hdl.handle.net/1822/2181 |
url |
https://hdl.handle.net/1822/2181 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Alves, M. J., Azoia, N. G., Bickley, J. F., Fortes, A. G., Gilchrist, T. L., & Mendonça, R. (2001). Diels–Alder reactions of alkyl 2H-azirine-3-carboxylates with furans. Journal of the Chemical Society, Perkin Transactions 1. Royal Society of Chemistry (RSC). http://doi.org/10.1039/b106985n 1472-7781 10.1039/b106985n |
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 |
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) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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