Reaction between N-alkylhydroxylamines and chiral enoate esters: More experimental evidence for a cycloaddition-like process, a rationale based on DFT theoretical calculations, and...

Autores
Moglioni, Albertina Gladys; Muray, Elena; Castillo, José A.; Álvarez Larena, Ángel; Moltrasio, Graciela Y.; Branchadell, Vicenç; Ortuño, Rosa M.
Año de publicación
2002
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The reactions between N-benzyl- and N-methylhydroxylamine and chiral enoate esters, derived from D-glyceraldehyde and (-)-verbenone, respectively, have been investigated. Theoretical calculations show that the most favorable mechanism involves the concerted cycloaddition of the hydroxylamine to the substrate. This result is in good agreement with the stereospecificity observed when the trisubstituted olefins are used. The open-chain adducts have been isolated when the processes are carried out at low temperatures and for short reaction times. These compounds evolve to the corresponding isoxazolidinones on standing at room temperature or under acid catalysis. The high π-facial diastereoselection has been rationalized on the basis of steric effects induced by the dioxolane ring for D-glyceraldehyde derivatives or by the cyclobutane gem-dimethyl substitution for esters prepared from (-)-verbenone. As an application of these reactions, new β-amino acids have been synthesized in a highly efficient and stereocontrolled manner.
Fil: Moglioni, Albertina Gladys. Universitat Autònoma de Barcelona; España. Universidad de Buenos Aires; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentina
Fil: Muray, Elena. Universitat Autònoma de Barcelona; España
Fil: Castillo, José A.. Universitat Autònoma de Barcelona; España
Fil: Álvarez Larena, Ángel. Universitat Autònoma de Barcelona; España
Fil: Moltrasio, Graciela Y.. Universidad de Buenos Aires; Argentina
Fil: Branchadell, Vicenç. Universitat Autònoma de Barcelona; España
Fil: Ortuño, Rosa M.. Universitat Autònoma de Barcelona; España
Materia
(-)-verbenone
chiral enoate esters
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/138276
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/138276
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Reaction between N-alkylhydroxylamines and chiral enoate esters: More experimental evidence for a cycloaddition-like process, a rationale based on DFT theoretical calculations, and stereoselective synthesis of new enantiopure β-amino acidsMoglioni, Albertina GladysMuray, ElenaCastillo, José A.Álvarez Larena, ÁngelMoltrasio, Graciela Y.Branchadell, VicençOrtuño, Rosa M.(-)-verbenonechiral enoate estershttps://purl.org/becyt/ford/3.1https://purl.org/becyt/ford/3The reactions between N-benzyl- and N-methylhydroxylamine and chiral enoate esters, derived from D-glyceraldehyde and (-)-verbenone, respectively, have been investigated. Theoretical calculations show that the most favorable mechanism involves the concerted cycloaddition of the hydroxylamine to the substrate. This result is in good agreement with the stereospecificity observed when the trisubstituted olefins are used. The open-chain adducts have been isolated when the processes are carried out at low temperatures and for short reaction times. These compounds evolve to the corresponding isoxazolidinones on standing at room temperature or under acid catalysis. The high π-facial diastereoselection has been rationalized on the basis of steric effects induced by the dioxolane ring for D-glyceraldehyde derivatives or by the cyclobutane gem-dimethyl substitution for esters prepared from (-)-verbenone. As an application of these reactions, new β-amino acids have been synthesized in a highly efficient and stereocontrolled manner.Fil: Moglioni, Albertina Gladys. Universitat Autònoma de Barcelona; España. Universidad de Buenos Aires; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; ArgentinaFil: Muray, Elena. Universitat Autònoma de Barcelona; EspañaFil: Castillo, José A.. Universitat Autònoma de Barcelona; EspañaFil: Álvarez Larena, Ángel. Universitat Autònoma de Barcelona; EspañaFil: Moltrasio, Graciela Y.. Universidad de Buenos Aires; ArgentinaFil: Branchadell, Vicenç. Universitat Autònoma de Barcelona; EspañaFil: Ortuño, Rosa M.. Universitat Autònoma de Barcelona; EspañaAmerican Chemical Society2002-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/138276Moglioni, Albertina Gladys; Muray, Elena; Castillo, José A.; Álvarez Larena, Ángel; Moltrasio, Graciela Y.; et al.; Reaction between N-alkylhydroxylamines and chiral enoate esters: More experimental evidence for a cycloaddition-like process, a rationale based on DFT theoretical calculations, and stereoselective synthesis of new enantiopure β-amino acids; American Chemical Society; Journal of Organic Chemistry; 67; 8; 12-2002; 2402-24100022-3263CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jo0159082info:eu-repo/semantics/altIdentifier/doi/10.1021/jo0159082info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:26:33Zoai:ri.conicet.gov.ar:11336/138276instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-15 14:26:34.248CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Reaction between N-alkylhydroxylamines and chiral enoate esters: More experimental evidence for a cycloaddition-like process, a rationale based on DFT theoretical calculations, and stereoselective synthesis of new enantiopure β-amino acids
title Reaction between N-alkylhydroxylamines and chiral enoate esters: More experimental evidence for a cycloaddition-like process, a rationale based on DFT theoretical calculations, and stereoselective synthesis of new enantiopure β-amino acids
spellingShingle Reaction between N-alkylhydroxylamines and chiral enoate esters: More experimental evidence for a cycloaddition-like process, a rationale based on DFT theoretical calculations, and stereoselective synthesis of new enantiopure β-amino acids
Moglioni, Albertina Gladys
(-)-verbenone
chiral enoate esters
title_short Reaction between N-alkylhydroxylamines and chiral enoate esters: More experimental evidence for a cycloaddition-like process, a rationale based on DFT theoretical calculations, and stereoselective synthesis of new enantiopure β-amino acids
title_full Reaction between N-alkylhydroxylamines and chiral enoate esters: More experimental evidence for a cycloaddition-like process, a rationale based on DFT theoretical calculations, and stereoselective synthesis of new enantiopure β-amino acids
title_fullStr Reaction between N-alkylhydroxylamines and chiral enoate esters: More experimental evidence for a cycloaddition-like process, a rationale based on DFT theoretical calculations, and stereoselective synthesis of new enantiopure β-amino acids
title_full_unstemmed Reaction between N-alkylhydroxylamines and chiral enoate esters: More experimental evidence for a cycloaddition-like process, a rationale based on DFT theoretical calculations, and stereoselective synthesis of new enantiopure β-amino acids
title_sort Reaction between N-alkylhydroxylamines and chiral enoate esters: More experimental evidence for a cycloaddition-like process, a rationale based on DFT theoretical calculations, and stereoselective synthesis of new enantiopure β-amino acids
dc.creator.none.fl_str_mv Moglioni, Albertina Gladys
Muray, Elena
Castillo, José A.
Álvarez Larena, Ángel
Moltrasio, Graciela Y.
Branchadell, Vicenç
Ortuño, Rosa M.
author Moglioni, Albertina Gladys
author_facet Moglioni, Albertina Gladys
Muray, Elena
Castillo, José A.
Álvarez Larena, Ángel
Moltrasio, Graciela Y.
Branchadell, Vicenç
Ortuño, Rosa M.
author_role author
author2 Muray, Elena
Castillo, José A.
Álvarez Larena, Ángel
Moltrasio, Graciela Y.
Branchadell, Vicenç
Ortuño, Rosa M.
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv (-)-verbenone
chiral enoate esters
topic (-)-verbenone
chiral enoate esters
purl_subject.fl_str_mv https://purl.org/becyt/ford/3.1
https://purl.org/becyt/ford/3
dc.description.none.fl_txt_mv The reactions between N-benzyl- and N-methylhydroxylamine and chiral enoate esters, derived from D-glyceraldehyde and (-)-verbenone, respectively, have been investigated. Theoretical calculations show that the most favorable mechanism involves the concerted cycloaddition of the hydroxylamine to the substrate. This result is in good agreement with the stereospecificity observed when the trisubstituted olefins are used. The open-chain adducts have been isolated when the processes are carried out at low temperatures and for short reaction times. These compounds evolve to the corresponding isoxazolidinones on standing at room temperature or under acid catalysis. The high π-facial diastereoselection has been rationalized on the basis of steric effects induced by the dioxolane ring for D-glyceraldehyde derivatives or by the cyclobutane gem-dimethyl substitution for esters prepared from (-)-verbenone. As an application of these reactions, new β-amino acids have been synthesized in a highly efficient and stereocontrolled manner.
Fil: Moglioni, Albertina Gladys. Universitat Autònoma de Barcelona; España. Universidad de Buenos Aires; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentina
Fil: Muray, Elena. Universitat Autònoma de Barcelona; España
Fil: Castillo, José A.. Universitat Autònoma de Barcelona; España
Fil: Álvarez Larena, Ángel. Universitat Autònoma de Barcelona; España
Fil: Moltrasio, Graciela Y.. Universidad de Buenos Aires; Argentina
Fil: Branchadell, Vicenç. Universitat Autònoma de Barcelona; España
Fil: Ortuño, Rosa M.. Universitat Autònoma de Barcelona; España
description The reactions between N-benzyl- and N-methylhydroxylamine and chiral enoate esters, derived from D-glyceraldehyde and (-)-verbenone, respectively, have been investigated. Theoretical calculations show that the most favorable mechanism involves the concerted cycloaddition of the hydroxylamine to the substrate. This result is in good agreement with the stereospecificity observed when the trisubstituted olefins are used. The open-chain adducts have been isolated when the processes are carried out at low temperatures and for short reaction times. These compounds evolve to the corresponding isoxazolidinones on standing at room temperature or under acid catalysis. The high π-facial diastereoselection has been rationalized on the basis of steric effects induced by the dioxolane ring for D-glyceraldehyde derivatives or by the cyclobutane gem-dimethyl substitution for esters prepared from (-)-verbenone. As an application of these reactions, new β-amino acids have been synthesized in a highly efficient and stereocontrolled manner.
publishDate 2002
dc.date.none.fl_str_mv 2002-12
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/138276
Moglioni, Albertina Gladys; Muray, Elena; Castillo, José A.; Álvarez Larena, Ángel; Moltrasio, Graciela Y.; et al.; Reaction between N-alkylhydroxylamines and chiral enoate esters: More experimental evidence for a cycloaddition-like process, a rationale based on DFT theoretical calculations, and stereoselective synthesis of new enantiopure β-amino acids; American Chemical Society; Journal of Organic Chemistry; 67; 8; 12-2002; 2402-2410
0022-3263
CONICET Digital
CONICET
url http://hdl.handle.net/11336/138276
identifier_str_mv Moglioni, Albertina Gladys; Muray, Elena; Castillo, José A.; Álvarez Larena, Ángel; Moltrasio, Graciela Y.; et al.; Reaction between N-alkylhydroxylamines and chiral enoate esters: More experimental evidence for a cycloaddition-like process, a rationale based on DFT theoretical calculations, and stereoselective synthesis of new enantiopure β-amino acids; American Chemical Society; Journal of Organic Chemistry; 67; 8; 12-2002; 2402-2410
0022-3263
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jo0159082
info:eu-repo/semantics/altIdentifier/doi/10.1021/jo0159082
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.22299

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