Stereospecific Synthesis of Pyrrolidines with Varied Configurations via 1,3-Dipolar Cycloadditions to Sugar-Derived Enones

Autores
Oliveira Udry, Guillermo Alejandro; Repetto, Evangelina; Varela, Oscar Jose
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Enantiomerically pure pyrrolidines have been obtained by 1,3-dipolar cycloaddition of stabilized azomethine ylides and sugar enones (dihydropyranones) derived from pentoses. Thus, the S-enone (menthyl 3,4-dideoxy-(1S)-pent-3-enopyranosid-2-ulose) was prepared from d-xylose, while the R analogue was obtained from l-arabinose. The dipoles were generated in situ from α-arylimino esters of common amino acids (glycine, alanine, or phenylalanine) and aromatic aldehydes (benzaldehyde, 3-formylpyridine and 4-methoxybenzaldehyde). Under optimized conditions, the cycloaddition reactions were highly diastereo- and regioselective to yield, in most of the cases, a very major adduct of the 16 theoretically possible. The diastereoselectivity relies on the strict stereocontrol exerted by the stereogenic center of the pyranone. Thus, the (S)-enone, derived from d-xylose, gave tetrasubstituted pyrrolidines having a defined stereochemistry for the four stereocenters of the ring, while they had the opposite configuration when starting from the (R)-dihydropyranone. Furthermore, some endo-cycloadducts underwent isomerization of the carbons vicinal to the nitrogen atom to afford pyrrolidines with a rather unusual stereochemistry for the direct dipolar cycloadditions.
Fil: Oliveira Udry, Guillermo Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones En Hidratos de Carbono; Argentina
Fil: Repetto, Evangelina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones En Hidratos de Carbono; Argentina
Fil: Varela, Oscar Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones En Hidratos de Carbono; Argentina
Materia
Pyrrolidines
1,3-Dipolar Cycloaddition
Diasteroselectivity
Stereochemistry
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:11336/8152
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Stereospecific Synthesis of Pyrrolidines with Varied Configurations via 1,3-Dipolar Cycloadditions to Sugar-Derived EnonesOliveira Udry, Guillermo AlejandroRepetto, EvangelinaVarela, Oscar JosePyrrolidines1,3-Dipolar CycloadditionDiasteroselectivityStereochemistryhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Enantiomerically pure pyrrolidines have been obtained by 1,3-dipolar cycloaddition of stabilized azomethine ylides and sugar enones (dihydropyranones) derived from pentoses. Thus, the S-enone (menthyl 3,4-dideoxy-(1S)-pent-3-enopyranosid-2-ulose) was prepared from d-xylose, while the R analogue was obtained from l-arabinose. The dipoles were generated in situ from α-arylimino esters of common amino acids (glycine, alanine, or phenylalanine) and aromatic aldehydes (benzaldehyde, 3-formylpyridine and 4-methoxybenzaldehyde). Under optimized conditions, the cycloaddition reactions were highly diastereo- and regioselective to yield, in most of the cases, a very major adduct of the 16 theoretically possible. The diastereoselectivity relies on the strict stereocontrol exerted by the stereogenic center of the pyranone. Thus, the (S)-enone, derived from d-xylose, gave tetrasubstituted pyrrolidines having a defined stereochemistry for the four stereocenters of the ring, while they had the opposite configuration when starting from the (R)-dihydropyranone. Furthermore, some endo-cycloadducts underwent isomerization of the carbons vicinal to the nitrogen atom to afford pyrrolidines with a rather unusual stereochemistry for the direct dipolar cycloadditions.Fil: Oliveira Udry, Guillermo Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones En Hidratos de Carbono; ArgentinaFil: Repetto, Evangelina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones En Hidratos de Carbono; ArgentinaFil: Varela, Oscar Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones En Hidratos de Carbono; ArgentinaAmerican Chemical Society2014-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/8152Oliveira Udry, Guillermo Alejandro; Repetto, Evangelina; Varela, Oscar Jose; Stereospecific Synthesis of Pyrrolidines with Varied Configurations via 1,3-Dipolar Cycloadditions to Sugar-Derived Enones; American Chemical Society; Journal Of Organic Chemistry; 79; 11; 5-2014; 4992-50060022-3263enginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jo500547yinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jo500547yinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:08:00Zoai:ri.conicet.gov.ar:11336/8152instacron: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 15:08:00.627CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Stereospecific Synthesis of Pyrrolidines with Varied Configurations via 1,3-Dipolar Cycloadditions to Sugar-Derived Enones
title Stereospecific Synthesis of Pyrrolidines with Varied Configurations via 1,3-Dipolar Cycloadditions to Sugar-Derived Enones
spellingShingle Stereospecific Synthesis of Pyrrolidines with Varied Configurations via 1,3-Dipolar Cycloadditions to Sugar-Derived Enones
Oliveira Udry, Guillermo Alejandro
Pyrrolidines
1,3-Dipolar Cycloaddition
Diasteroselectivity
Stereochemistry
title_short Stereospecific Synthesis of Pyrrolidines with Varied Configurations via 1,3-Dipolar Cycloadditions to Sugar-Derived Enones
title_full Stereospecific Synthesis of Pyrrolidines with Varied Configurations via 1,3-Dipolar Cycloadditions to Sugar-Derived Enones
title_fullStr Stereospecific Synthesis of Pyrrolidines with Varied Configurations via 1,3-Dipolar Cycloadditions to Sugar-Derived Enones
title_full_unstemmed Stereospecific Synthesis of Pyrrolidines with Varied Configurations via 1,3-Dipolar Cycloadditions to Sugar-Derived Enones
title_sort Stereospecific Synthesis of Pyrrolidines with Varied Configurations via 1,3-Dipolar Cycloadditions to Sugar-Derived Enones
dc.creator.none.fl_str_mv Oliveira Udry, Guillermo Alejandro
Repetto, Evangelina
Varela, Oscar Jose
author Oliveira Udry, Guillermo Alejandro
author_facet Oliveira Udry, Guillermo Alejandro
Repetto, Evangelina
Varela, Oscar Jose
author_role author
author2 Repetto, Evangelina
Varela, Oscar Jose
author2_role author
author
dc.subject.none.fl_str_mv Pyrrolidines
1,3-Dipolar Cycloaddition
Diasteroselectivity
Stereochemistry
topic Pyrrolidines
1,3-Dipolar Cycloaddition
Diasteroselectivity
Stereochemistry
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Enantiomerically pure pyrrolidines have been obtained by 1,3-dipolar cycloaddition of stabilized azomethine ylides and sugar enones (dihydropyranones) derived from pentoses. Thus, the S-enone (menthyl 3,4-dideoxy-(1S)-pent-3-enopyranosid-2-ulose) was prepared from d-xylose, while the R analogue was obtained from l-arabinose. The dipoles were generated in situ from α-arylimino esters of common amino acids (glycine, alanine, or phenylalanine) and aromatic aldehydes (benzaldehyde, 3-formylpyridine and 4-methoxybenzaldehyde). Under optimized conditions, the cycloaddition reactions were highly diastereo- and regioselective to yield, in most of the cases, a very major adduct of the 16 theoretically possible. The diastereoselectivity relies on the strict stereocontrol exerted by the stereogenic center of the pyranone. Thus, the (S)-enone, derived from d-xylose, gave tetrasubstituted pyrrolidines having a defined stereochemistry for the four stereocenters of the ring, while they had the opposite configuration when starting from the (R)-dihydropyranone. Furthermore, some endo-cycloadducts underwent isomerization of the carbons vicinal to the nitrogen atom to afford pyrrolidines with a rather unusual stereochemistry for the direct dipolar cycloadditions.
Fil: Oliveira Udry, Guillermo Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones En Hidratos de Carbono; Argentina
Fil: Repetto, Evangelina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones En Hidratos de Carbono; Argentina
Fil: Varela, Oscar Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones En Hidratos de Carbono; Argentina
description Enantiomerically pure pyrrolidines have been obtained by 1,3-dipolar cycloaddition of stabilized azomethine ylides and sugar enones (dihydropyranones) derived from pentoses. Thus, the S-enone (menthyl 3,4-dideoxy-(1S)-pent-3-enopyranosid-2-ulose) was prepared from d-xylose, while the R analogue was obtained from l-arabinose. The dipoles were generated in situ from α-arylimino esters of common amino acids (glycine, alanine, or phenylalanine) and aromatic aldehydes (benzaldehyde, 3-formylpyridine and 4-methoxybenzaldehyde). Under optimized conditions, the cycloaddition reactions were highly diastereo- and regioselective to yield, in most of the cases, a very major adduct of the 16 theoretically possible. The diastereoselectivity relies on the strict stereocontrol exerted by the stereogenic center of the pyranone. Thus, the (S)-enone, derived from d-xylose, gave tetrasubstituted pyrrolidines having a defined stereochemistry for the four stereocenters of the ring, while they had the opposite configuration when starting from the (R)-dihydropyranone. Furthermore, some endo-cycloadducts underwent isomerization of the carbons vicinal to the nitrogen atom to afford pyrrolidines with a rather unusual stereochemistry for the direct dipolar cycloadditions.
publishDate 2014
dc.date.none.fl_str_mv 2014-05
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/11336/8152
Oliveira Udry, Guillermo Alejandro; Repetto, Evangelina; Varela, Oscar Jose; Stereospecific Synthesis of Pyrrolidines with Varied Configurations via 1,3-Dipolar Cycloadditions to Sugar-Derived Enones; American Chemical Society; Journal Of Organic Chemistry; 79; 11; 5-2014; 4992-5006
0022-3263
url http://hdl.handle.net/11336/8152
identifier_str_mv Oliveira Udry, Guillermo Alejandro; Repetto, Evangelina; Varela, Oscar Jose; Stereospecific Synthesis of Pyrrolidines with Varied Configurations via 1,3-Dipolar Cycloadditions to Sugar-Derived Enones; American Chemical Society; Journal Of Organic Chemistry; 79; 11; 5-2014; 4992-5006
0022-3263
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jo500547y
info:eu-repo/semantics/altIdentifier/doi/10.1021/jo500547y
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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