Synthesis of (1→3) Thiodisaccharides of GlcNAc and the Serendipitous Formation of 2,3-Dideoxy-(1→2)-thiodisaccharides through a Vinyl Azide Intermediate

Autores
Cristófalo, Alejandro Ezequiel; Nieto, Pedro M.; Uhrig, Maria Laura
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The syntheses of β-S-GlcA(1→3)GlcNAc and β-S-Gal(1→3)GlcNAc thiodisaccharides, which can be considered mimetics of the repeating units of hyaluronan and keratan respectively, were achieved by SN2 displacement of a triflate group allocated at the 3-position of a convenient 2- azido-4,6-O-benzylidene-2-deoxy-β-D-allopyranose precursor by the corresponding nucleophilic suitable protected thioaldoses derived from glucuronic acid (GlcA) and galactose (Gal). The study of the reaction led to the finding that the vinyl azide formed by competitive E2 reaction of the mentioned triflate was an interesting precursor of a new kind of 2,3-dideoxy-2-azido-(1→2) thiodisaccharides through an addition reaction. Determination of the stereochemistry of the new stereocenter at C-2 was achieved by NOESY experiments. Final protecting group manipulation of the (1→3) thiodisaccharides led to a family of derivatives that could be used as building blocks for the synthesis of complex glycomimetics.
Fil: Cristófalo, Alejandro Ezequiel. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. 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: Nieto, Pedro M.. Universidad de Sevilla; España. Consejo Superior de Investigaciones Científicas; España
Fil: Uhrig, Maria Laura. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. 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
Materia
N-ACETYLGLUCOSAMINE
THIODISACCHARIDES
VINYL AZIDE
HYALURONAN
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:11336/151258
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/151258
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Synthesis of (1→3) Thiodisaccharides of GlcNAc and the Serendipitous Formation of 2,3-Dideoxy-(1→2)-thiodisaccharides through a Vinyl Azide IntermediateCristófalo, Alejandro EzequielNieto, Pedro M.Uhrig, Maria LauraN-ACETYLGLUCOSAMINETHIODISACCHARIDESVINYL AZIDEHYALURONANhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The syntheses of β-S-GlcA(1→3)GlcNAc and β-S-Gal(1→3)GlcNAc thiodisaccharides, which can be considered mimetics of the repeating units of hyaluronan and keratan respectively, were achieved by SN2 displacement of a triflate group allocated at the 3-position of a convenient 2- azido-4,6-O-benzylidene-2-deoxy-β-D-allopyranose precursor by the corresponding nucleophilic suitable protected thioaldoses derived from glucuronic acid (GlcA) and galactose (Gal). The study of the reaction led to the finding that the vinyl azide formed by competitive E2 reaction of the mentioned triflate was an interesting precursor of a new kind of 2,3-dideoxy-2-azido-(1→2) thiodisaccharides through an addition reaction. Determination of the stereochemistry of the new stereocenter at C-2 was achieved by NOESY experiments. Final protecting group manipulation of the (1→3) thiodisaccharides led to a family of derivatives that could be used as building blocks for the synthesis of complex glycomimetics.Fil: Cristófalo, Alejandro Ezequiel. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. 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: Nieto, Pedro M.. Universidad de Sevilla; España. Consejo Superior de Investigaciones Científicas; EspañaFil: Uhrig, Maria Laura. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. 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; ArgentinaAmerican Chemical Society2019-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/151258Cristófalo, Alejandro Ezequiel; Nieto, Pedro M.; Uhrig, Maria Laura; Synthesis of (1→3) Thiodisaccharides of GlcNAc and the Serendipitous Formation of 2,3-Dideoxy-(1→2)-thiodisaccharides through a Vinyl Azide Intermediate; American Chemical Society; Journal of Organic Chemistry; 85; 2; 12-2019; 306-3170022-3263CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/acs.joc.9b01883info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.joc.9b01883info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:54:36Zoai:ri.conicet.gov.ar:11336/151258instacron: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:34982025-09-03 09:54:36.313CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Synthesis of (1→3) Thiodisaccharides of GlcNAc and the Serendipitous Formation of 2,3-Dideoxy-(1→2)-thiodisaccharides through a Vinyl Azide Intermediate
title Synthesis of (1→3) Thiodisaccharides of GlcNAc and the Serendipitous Formation of 2,3-Dideoxy-(1→2)-thiodisaccharides through a Vinyl Azide Intermediate
spellingShingle Synthesis of (1→3) Thiodisaccharides of GlcNAc and the Serendipitous Formation of 2,3-Dideoxy-(1→2)-thiodisaccharides through a Vinyl Azide Intermediate
Cristófalo, Alejandro Ezequiel
N-ACETYLGLUCOSAMINE
THIODISACCHARIDES
VINYL AZIDE
HYALURONAN
title_short Synthesis of (1→3) Thiodisaccharides of GlcNAc and the Serendipitous Formation of 2,3-Dideoxy-(1→2)-thiodisaccharides through a Vinyl Azide Intermediate
title_full Synthesis of (1→3) Thiodisaccharides of GlcNAc and the Serendipitous Formation of 2,3-Dideoxy-(1→2)-thiodisaccharides through a Vinyl Azide Intermediate
title_fullStr Synthesis of (1→3) Thiodisaccharides of GlcNAc and the Serendipitous Formation of 2,3-Dideoxy-(1→2)-thiodisaccharides through a Vinyl Azide Intermediate
title_full_unstemmed Synthesis of (1→3) Thiodisaccharides of GlcNAc and the Serendipitous Formation of 2,3-Dideoxy-(1→2)-thiodisaccharides through a Vinyl Azide Intermediate
title_sort Synthesis of (1→3) Thiodisaccharides of GlcNAc and the Serendipitous Formation of 2,3-Dideoxy-(1→2)-thiodisaccharides through a Vinyl Azide Intermediate
dc.creator.none.fl_str_mv Cristófalo, Alejandro Ezequiel
Nieto, Pedro M.
Uhrig, Maria Laura
author Cristófalo, Alejandro Ezequiel
author_facet Cristófalo, Alejandro Ezequiel
Nieto, Pedro M.
Uhrig, Maria Laura
author_role author
author2 Nieto, Pedro M.
Uhrig, Maria Laura
author2_role author
author
dc.subject.none.fl_str_mv N-ACETYLGLUCOSAMINE
THIODISACCHARIDES
VINYL AZIDE
HYALURONAN
topic N-ACETYLGLUCOSAMINE
THIODISACCHARIDES
VINYL AZIDE
HYALURONAN
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The syntheses of β-S-GlcA(1→3)GlcNAc and β-S-Gal(1→3)GlcNAc thiodisaccharides, which can be considered mimetics of the repeating units of hyaluronan and keratan respectively, were achieved by SN2 displacement of a triflate group allocated at the 3-position of a convenient 2- azido-4,6-O-benzylidene-2-deoxy-β-D-allopyranose precursor by the corresponding nucleophilic suitable protected thioaldoses derived from glucuronic acid (GlcA) and galactose (Gal). The study of the reaction led to the finding that the vinyl azide formed by competitive E2 reaction of the mentioned triflate was an interesting precursor of a new kind of 2,3-dideoxy-2-azido-(1→2) thiodisaccharides through an addition reaction. Determination of the stereochemistry of the new stereocenter at C-2 was achieved by NOESY experiments. Final protecting group manipulation of the (1→3) thiodisaccharides led to a family of derivatives that could be used as building blocks for the synthesis of complex glycomimetics.
Fil: Cristófalo, Alejandro Ezequiel. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. 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: Nieto, Pedro M.. Universidad de Sevilla; España. Consejo Superior de Investigaciones Científicas; España
Fil: Uhrig, Maria Laura. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. 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
description The syntheses of β-S-GlcA(1→3)GlcNAc and β-S-Gal(1→3)GlcNAc thiodisaccharides, which can be considered mimetics of the repeating units of hyaluronan and keratan respectively, were achieved by SN2 displacement of a triflate group allocated at the 3-position of a convenient 2- azido-4,6-O-benzylidene-2-deoxy-β-D-allopyranose precursor by the corresponding nucleophilic suitable protected thioaldoses derived from glucuronic acid (GlcA) and galactose (Gal). The study of the reaction led to the finding that the vinyl azide formed by competitive E2 reaction of the mentioned triflate was an interesting precursor of a new kind of 2,3-dideoxy-2-azido-(1→2) thiodisaccharides through an addition reaction. Determination of the stereochemistry of the new stereocenter at C-2 was achieved by NOESY experiments. Final protecting group manipulation of the (1→3) thiodisaccharides led to a family of derivatives that could be used as building blocks for the synthesis of complex glycomimetics.
publishDate 2019
dc.date.none.fl_str_mv 2019-12
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/11336/151258
Cristófalo, Alejandro Ezequiel; Nieto, Pedro M.; Uhrig, Maria Laura; Synthesis of (1→3) Thiodisaccharides of GlcNAc and the Serendipitous Formation of 2,3-Dideoxy-(1→2)-thiodisaccharides through a Vinyl Azide Intermediate; American Chemical Society; Journal of Organic Chemistry; 85; 2; 12-2019; 306-317
0022-3263
CONICET Digital
CONICET
url http://hdl.handle.net/11336/151258
identifier_str_mv Cristófalo, Alejandro Ezequiel; Nieto, Pedro M.; Uhrig, Maria Laura; Synthesis of (1→3) Thiodisaccharides of GlcNAc and the Serendipitous Formation of 2,3-Dideoxy-(1→2)-thiodisaccharides through a Vinyl Azide Intermediate; American Chemical Society; Journal of Organic Chemistry; 85; 2; 12-2019; 306-317
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/abs/10.1021/acs.joc.9b01883
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.joc.9b01883
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
_version_ 1842269295365586944
score 13.13397

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