A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors

Autores
Colombo, María Inés; Stortz, Carlos Arturo; Ruveda, Edmundo
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Four isomeric N-dimethylmaleoyl 4,6-O-benzylidene-protected d-hexosamine acceptors (2, 3, 4, and 5) with all possible configurations at C-1 and C-3 (e.g., derived from d-glucosamine and d-allosamine) were prepared, and the assessment of their O-3 relative reactivity through competition experiments using the known per-O-acetylated d-galactopyranosyl trichloroacetimidate donor (15) was then carried out. The reactivities are in the order 4 ≫ 2 > 5 > 3. The analysis of the NMR spectra of 2-5 at different temperature and modeling experiments carried out on analogs of 2-5 (DFT) and on the acceptors themselves (MM) are coincident, and have helped to establish the stability of the different hydrogen bonds, and of the conformers which carry them. The whole results suggest that the electronic effects (hydrogen bonds) are required to explain the observed trend, in spite of the axial conformation of the most reactive hydroxyl group. The steric effects appear only when hydrogen bonds are weak.
Fil: Colombo, María Inés. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Fil: Stortz, Carlos Arturo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina
Fil: Ruveda, Edmundo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Materia
COMPETITIVE GLYCOSYLATIONS
GALACTOPYRANOSYL DONOR
GLUCOSAMINE/ALLOSAMINE ACCEPTORS
MOLECULAR MODELING
N-DIMETHYLMALEOYL GROUP
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:11336/99127
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/99127
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptorsColombo, María InésStortz, Carlos ArturoRuveda, EdmundoCOMPETITIVE GLYCOSYLATIONSGALACTOPYRANOSYL DONORGLUCOSAMINE/ALLOSAMINE ACCEPTORSMOLECULAR MODELINGN-DIMETHYLMALEOYL GROUPhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Four isomeric N-dimethylmaleoyl 4,6-O-benzylidene-protected d-hexosamine acceptors (2, 3, 4, and 5) with all possible configurations at C-1 and C-3 (e.g., derived from d-glucosamine and d-allosamine) were prepared, and the assessment of their O-3 relative reactivity through competition experiments using the known per-O-acetylated d-galactopyranosyl trichloroacetimidate donor (15) was then carried out. The reactivities are in the order 4 ≫ 2 > 5 > 3. The analysis of the NMR spectra of 2-5 at different temperature and modeling experiments carried out on analogs of 2-5 (DFT) and on the acceptors themselves (MM) are coincident, and have helped to establish the stability of the different hydrogen bonds, and of the conformers which carry them. The whole results suggest that the electronic effects (hydrogen bonds) are required to explain the observed trend, in spite of the axial conformation of the most reactive hydroxyl group. The steric effects appear only when hydrogen bonds are weak.Fil: Colombo, María Inés. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; ArgentinaFil: Stortz, Carlos Arturo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Ruveda, Edmundo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; ArgentinaElsevier2011-04info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/99127Colombo, María Inés; Stortz, Carlos Arturo; Ruveda, Edmundo; A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors; Elsevier; Carbohydrate Research; 346; 5; 4-2011; 569-5760008-6215CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0008621511000292info:eu-repo/semantics/altIdentifier/doi/10.1016/j.carres.2011.01.017info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:24:06Zoai:ri.conicet.gov.ar:11336/99127instacron: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:34982025-09-10 13:24:06.32CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors
title A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors
spellingShingle A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors
Colombo, María Inés
COMPETITIVE GLYCOSYLATIONS
GALACTOPYRANOSYL DONOR
GLUCOSAMINE/ALLOSAMINE ACCEPTORS
MOLECULAR MODELING
N-DIMETHYLMALEOYL GROUP
title_short A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors
title_full A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors
title_fullStr A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors
title_full_unstemmed A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors
title_sort A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors
dc.creator.none.fl_str_mv Colombo, María Inés
Stortz, Carlos Arturo
Ruveda, Edmundo
author Colombo, María Inés
author_facet Colombo, María Inés
Stortz, Carlos Arturo
Ruveda, Edmundo
author_role author
author2 Stortz, Carlos Arturo
Ruveda, Edmundo
author2_role author
author
dc.subject.none.fl_str_mv COMPETITIVE GLYCOSYLATIONS
GALACTOPYRANOSYL DONOR
GLUCOSAMINE/ALLOSAMINE ACCEPTORS
MOLECULAR MODELING
N-DIMETHYLMALEOYL GROUP
topic COMPETITIVE GLYCOSYLATIONS
GALACTOPYRANOSYL DONOR
GLUCOSAMINE/ALLOSAMINE ACCEPTORS
MOLECULAR MODELING
N-DIMETHYLMALEOYL GROUP
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Four isomeric N-dimethylmaleoyl 4,6-O-benzylidene-protected d-hexosamine acceptors (2, 3, 4, and 5) with all possible configurations at C-1 and C-3 (e.g., derived from d-glucosamine and d-allosamine) were prepared, and the assessment of their O-3 relative reactivity through competition experiments using the known per-O-acetylated d-galactopyranosyl trichloroacetimidate donor (15) was then carried out. The reactivities are in the order 4 ≫ 2 > 5 > 3. The analysis of the NMR spectra of 2-5 at different temperature and modeling experiments carried out on analogs of 2-5 (DFT) and on the acceptors themselves (MM) are coincident, and have helped to establish the stability of the different hydrogen bonds, and of the conformers which carry them. The whole results suggest that the electronic effects (hydrogen bonds) are required to explain the observed trend, in spite of the axial conformation of the most reactive hydroxyl group. The steric effects appear only when hydrogen bonds are weak.
Fil: Colombo, María Inés. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Fil: Stortz, Carlos Arturo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina
Fil: Ruveda, Edmundo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
description Four isomeric N-dimethylmaleoyl 4,6-O-benzylidene-protected d-hexosamine acceptors (2, 3, 4, and 5) with all possible configurations at C-1 and C-3 (e.g., derived from d-glucosamine and d-allosamine) were prepared, and the assessment of their O-3 relative reactivity through competition experiments using the known per-O-acetylated d-galactopyranosyl trichloroacetimidate donor (15) was then carried out. The reactivities are in the order 4 ≫ 2 > 5 > 3. The analysis of the NMR spectra of 2-5 at different temperature and modeling experiments carried out on analogs of 2-5 (DFT) and on the acceptors themselves (MM) are coincident, and have helped to establish the stability of the different hydrogen bonds, and of the conformers which carry them. The whole results suggest that the electronic effects (hydrogen bonds) are required to explain the observed trend, in spite of the axial conformation of the most reactive hydroxyl group. The steric effects appear only when hydrogen bonds are weak.
publishDate 2011
dc.date.none.fl_str_mv 2011-04
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/11336/99127
Colombo, María Inés; Stortz, Carlos Arturo; Ruveda, Edmundo; A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors; Elsevier; Carbohydrate Research; 346; 5; 4-2011; 569-576
0008-6215
CONICET Digital
CONICET
url http://hdl.handle.net/11336/99127
identifier_str_mv Colombo, María Inés; Stortz, Carlos Arturo; Ruveda, Edmundo; A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors; Elsevier; Carbohydrate Research; 346; 5; 4-2011; 569-576
0008-6215
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://www.sciencedirect.com/science/article/pii/S0008621511000292
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.carres.2011.01.017
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
application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
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 12.48226

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