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
Autor(a) principal: | |
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Data de Publicação: | 1999 |
Outros Autores: | |
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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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 |
format |
article |
status_str |
publishedVersion |
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) instacron:SBQ |
instname_str |
Sociedade Brasileira de Química (SBQ) |
instacron_str |
SBQ |
institution |
SBQ |
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) |
repository.mail.fl_str_mv |
||office@jbcs.sbq.org.br |
_version_ |
1750318163769163776 |