Rhodium(II)-Catalysed Intramolecular O-H Insertion of alpha-Diazo-gamma-Azido-delta-Hydroxy-beta-Ketoesters: Evidence for a Novel Sigmatropic Rearrangement of an Allylic Azide Intermediate

Detalhes bibliográficos
Autor(a) principal: Padwa,Albert
Data de Publicação: 1999
Outros Autores: Sá,Marcus Mandolesi
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=S0103-50531999000300012
Resumo: The Rh2(OAc)4 catalyzed intramolecular O-H insertion reaction of delta-hydroxy-alpha-diazoesters affords 3(2H)-furanone-2-carboxylates in good yield but with moderate selectivity (d.e. ca 60%). The initially formed 2,5-substituted cis-furanones were found to epimerize to the corresponding 2,5-trans isomers when subjected to silica gel chromatography. The Rh2(OAc)4 catalyzed decomposition of gamma-azido-delta-hydroxy-alpha-diazoesters also furnished 3(2H)-furanone-2-carboxylates. These compounds are derived by a sequential O-H insertion reaction followed by a concerted [3,3]-sigmatropic shift of the allylic azide intermediate.
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spelling Rhodium(II)-Catalysed Intramolecular O-H Insertion of alpha-Diazo-gamma-Azido-delta-Hydroxy-beta-Ketoesters: Evidence for a Novel Sigmatropic Rearrangement of an Allylic Azide Intermediatediazoestersintramolecular OH insertion3(2H)-furanonerhodium (II)The Rh2(OAc)4 catalyzed intramolecular O-H insertion reaction of delta-hydroxy-alpha-diazoesters affords 3(2H)-furanone-2-carboxylates in good yield but with moderate selectivity (d.e. ca 60%). The initially formed 2,5-substituted cis-furanones were found to epimerize to the corresponding 2,5-trans isomers when subjected to silica gel chromatography. The Rh2(OAc)4 catalyzed decomposition of gamma-azido-delta-hydroxy-alpha-diazoesters also furnished 3(2H)-furanone-2-carboxylates. These compounds are derived by a sequential O-H insertion reaction followed by a concerted [3,3]-sigmatropic shift of the allylic azide intermediate.Sociedade Brasileira de Química1999-01-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50531999000300012Journal of the Brazilian Chemical Society v.10 n.3 1999reponame:Journal of the Brazilian Chemical Society (Online)instname:Sociedade Brasileira de Química (SBQ)instacron:SBQ10.1590/S0103-50531999000300012info:eu-repo/semantics/openAccessPadwa,AlbertSá,Marcus Mandolesieng2002-10-23T00:00:00Zoai:scielo:S0103-50531999000300012Revistahttp://jbcs.sbq.org.brONGhttps://old.scielo.br/oai/scielo-oai.php||office@jbcs.sbq.org.br1678-47900103-5053opendoar:2002-10-23T00:00Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ)false
dc.title.none.fl_str_mv Rhodium(II)-Catalysed Intramolecular O-H Insertion of alpha-Diazo-gamma-Azido-delta-Hydroxy-beta-Ketoesters: Evidence for a Novel Sigmatropic Rearrangement of an Allylic Azide Intermediate
title Rhodium(II)-Catalysed Intramolecular O-H Insertion of alpha-Diazo-gamma-Azido-delta-Hydroxy-beta-Ketoesters: Evidence for a Novel Sigmatropic Rearrangement of an Allylic Azide Intermediate
spellingShingle Rhodium(II)-Catalysed Intramolecular O-H Insertion of alpha-Diazo-gamma-Azido-delta-Hydroxy-beta-Ketoesters: Evidence for a Novel Sigmatropic Rearrangement of an Allylic Azide Intermediate
Padwa,Albert
diazoesters
intramolecular OH insertion
3(2H)-furanone
rhodium (II)
title_short Rhodium(II)-Catalysed Intramolecular O-H Insertion of alpha-Diazo-gamma-Azido-delta-Hydroxy-beta-Ketoesters: Evidence for a Novel Sigmatropic Rearrangement of an Allylic Azide Intermediate
title_full Rhodium(II)-Catalysed Intramolecular O-H Insertion of alpha-Diazo-gamma-Azido-delta-Hydroxy-beta-Ketoesters: Evidence for a Novel Sigmatropic Rearrangement of an Allylic Azide Intermediate
title_fullStr Rhodium(II)-Catalysed Intramolecular O-H Insertion of alpha-Diazo-gamma-Azido-delta-Hydroxy-beta-Ketoesters: Evidence for a Novel Sigmatropic Rearrangement of an Allylic Azide Intermediate
title_full_unstemmed Rhodium(II)-Catalysed Intramolecular O-H Insertion of alpha-Diazo-gamma-Azido-delta-Hydroxy-beta-Ketoesters: Evidence for a Novel Sigmatropic Rearrangement of an Allylic Azide Intermediate
title_sort Rhodium(II)-Catalysed Intramolecular O-H Insertion of alpha-Diazo-gamma-Azido-delta-Hydroxy-beta-Ketoesters: Evidence for a Novel Sigmatropic Rearrangement of an Allylic Azide Intermediate
author Padwa,Albert
author_facet Padwa,Albert
Sá,Marcus Mandolesi
author_role author
author2 Sá,Marcus Mandolesi
author2_role author
dc.contributor.author.fl_str_mv Padwa,Albert
Sá,Marcus Mandolesi
dc.subject.por.fl_str_mv diazoesters
intramolecular OH insertion
3(2H)-furanone
rhodium (II)
topic diazoesters
intramolecular OH insertion
3(2H)-furanone
rhodium (II)
description The Rh2(OAc)4 catalyzed intramolecular O-H insertion reaction of delta-hydroxy-alpha-diazoesters affords 3(2H)-furanone-2-carboxylates in good yield but with moderate selectivity (d.e. ca 60%). The initially formed 2,5-substituted cis-furanones were found to epimerize to the corresponding 2,5-trans isomers when subjected to silica gel chromatography. The Rh2(OAc)4 catalyzed decomposition of gamma-azido-delta-hydroxy-alpha-diazoesters also furnished 3(2H)-furanone-2-carboxylates. These compounds are derived by a sequential O-H insertion reaction followed by a concerted [3,3]-sigmatropic shift of the allylic azide intermediate.
publishDate 1999
dc.date.none.fl_str_mv 1999-01-01
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
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dc.identifier.uri.fl_str_mv http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50531999000300012
url http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50531999000300012
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv 10.1590/S0103-50531999000300012
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.10 n.3 1999
reponame:Journal of the Brazilian Chemical Society (Online)
instname:Sociedade Brasileira de Química (SBQ)
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instname_str Sociedade Brasileira de Química (SBQ)
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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)
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