Conformationally restricted 3,5-O-(di-tert-butylsilylene)-D-galactofuranosyl thioglycoside donor for 1,2-cis a-D-galactofuranosylation

Autores
Tilve, Mariano Javier; Gallo, Carola
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
A conformationally restricted 2-O-benzyl-3,5-O-di-tert-butylsilylene-b-D-thiogalactofuranoside donor was prepared from benzyl alpha-D-galactofuranoside and its donor capability was studied for stereoselective 1,2-cis a-D-galactofuranosylation. An unusual chemical behavior on benzylation and hydrogenolysis reactions was observed after the introduction of the 3,5-O-di-tert-butylsilylene protecting group into the galactofuranosyl moiety. The influence of the solvent, temperature and activating system was evaluated. The NIS/AgOTf system, widely used in 1,2-cis b-arabinofuranosylation, was not satisfactory enough for 1,2-cis galactofuranosylation. However, moderate to high alpha-selectivity was obtained with all the acceptors employed when used p-NO2PhSCl/AgOTf as a promoting system, in CH2Cl2 at -78 ºC. The order of the addition of the reactants (premixing or preactivation) did not affect substantially the stereochemical course of the glycosylation reaction. The a-D-Galf-(1-6)-D-Man linkage was achieved with complete diastereoselectivity by preactivation of the conformationally constrained thioglycoside donor.
Fil: Tilve, Mariano Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono; Argentina
Fil: Gallo, Carola. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono; Argentina
Materia
Glycosylation
Thioglycoside
1,2-Cis
Galactofuranose
Solvent Effects
Protecting Groups
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/8158
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/8158
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Conformationally restricted 3,5-O-(di-tert-butylsilylene)-D-galactofuranosyl thioglycoside donor for 1,2-cis a-D-galactofuranosylationTilve, Mariano JavierGallo, CarolaGlycosylationThioglycoside1,2-CisGalactofuranoseSolvent EffectsProtecting Groupshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1A conformationally restricted 2-O-benzyl-3,5-O-di-tert-butylsilylene-b-D-thiogalactofuranoside donor was prepared from benzyl alpha-D-galactofuranoside and its donor capability was studied for stereoselective 1,2-cis a-D-galactofuranosylation. An unusual chemical behavior on benzylation and hydrogenolysis reactions was observed after the introduction of the 3,5-O-di-tert-butylsilylene protecting group into the galactofuranosyl moiety. The influence of the solvent, temperature and activating system was evaluated. The NIS/AgOTf system, widely used in 1,2-cis b-arabinofuranosylation, was not satisfactory enough for 1,2-cis galactofuranosylation. However, moderate to high alpha-selectivity was obtained with all the acceptors employed when used p-NO2PhSCl/AgOTf as a promoting system, in CH2Cl2 at -78 ºC. The order of the addition of the reactants (premixing or preactivation) did not affect substantially the stereochemical course of the glycosylation reaction. The a-D-Galf-(1-6)-D-Man linkage was achieved with complete diastereoselectivity by preactivation of the conformationally constrained thioglycoside donor.Fil: Tilve, Mariano Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Gallo, Carola. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono; ArgentinaElsevier2014-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/8158Tilve, Mariano Javier; Gallo, Carola; Conformationally restricted 3,5-O-(di-tert-butylsilylene)-D-galactofuranosyl thioglycoside donor for 1,2-cis a-D-galactofuranosylation; Elsevier; Carbohydrate Research; 397; 8-2014; 7-170008-6215enginfo:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0008621514003085info:eu-repo/semantics/altIdentifier/doi/10.1016/j.carres.2014.07.024info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:39:03Zoai:ri.conicet.gov.ar:11336/8158instacron: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 14:39:03.302CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Conformationally restricted 3,5-O-(di-tert-butylsilylene)-D-galactofuranosyl thioglycoside donor for 1,2-cis a-D-galactofuranosylation
title Conformationally restricted 3,5-O-(di-tert-butylsilylene)-D-galactofuranosyl thioglycoside donor for 1,2-cis a-D-galactofuranosylation
spellingShingle Conformationally restricted 3,5-O-(di-tert-butylsilylene)-D-galactofuranosyl thioglycoside donor for 1,2-cis a-D-galactofuranosylation
Tilve, Mariano Javier
Glycosylation
Thioglycoside
1,2-Cis
Galactofuranose
Solvent Effects
Protecting Groups
title_short Conformationally restricted 3,5-O-(di-tert-butylsilylene)-D-galactofuranosyl thioglycoside donor for 1,2-cis a-D-galactofuranosylation
title_full Conformationally restricted 3,5-O-(di-tert-butylsilylene)-D-galactofuranosyl thioglycoside donor for 1,2-cis a-D-galactofuranosylation
title_fullStr Conformationally restricted 3,5-O-(di-tert-butylsilylene)-D-galactofuranosyl thioglycoside donor for 1,2-cis a-D-galactofuranosylation
title_full_unstemmed Conformationally restricted 3,5-O-(di-tert-butylsilylene)-D-galactofuranosyl thioglycoside donor for 1,2-cis a-D-galactofuranosylation
title_sort Conformationally restricted 3,5-O-(di-tert-butylsilylene)-D-galactofuranosyl thioglycoside donor for 1,2-cis a-D-galactofuranosylation
dc.creator.none.fl_str_mv Tilve, Mariano Javier
Gallo, Carola
author Tilve, Mariano Javier
author_facet Tilve, Mariano Javier
Gallo, Carola
author_role author
author2 Gallo, Carola
author2_role author
dc.subject.none.fl_str_mv Glycosylation
Thioglycoside
1,2-Cis
Galactofuranose
Solvent Effects
Protecting Groups
topic Glycosylation
Thioglycoside
1,2-Cis
Galactofuranose
Solvent Effects
Protecting Groups
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv A conformationally restricted 2-O-benzyl-3,5-O-di-tert-butylsilylene-b-D-thiogalactofuranoside donor was prepared from benzyl alpha-D-galactofuranoside and its donor capability was studied for stereoselective 1,2-cis a-D-galactofuranosylation. An unusual chemical behavior on benzylation and hydrogenolysis reactions was observed after the introduction of the 3,5-O-di-tert-butylsilylene protecting group into the galactofuranosyl moiety. The influence of the solvent, temperature and activating system was evaluated. The NIS/AgOTf system, widely used in 1,2-cis b-arabinofuranosylation, was not satisfactory enough for 1,2-cis galactofuranosylation. However, moderate to high alpha-selectivity was obtained with all the acceptors employed when used p-NO2PhSCl/AgOTf as a promoting system, in CH2Cl2 at -78 ºC. The order of the addition of the reactants (premixing or preactivation) did not affect substantially the stereochemical course of the glycosylation reaction. The a-D-Galf-(1-6)-D-Man linkage was achieved with complete diastereoselectivity by preactivation of the conformationally constrained thioglycoside donor.
Fil: Tilve, Mariano Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono; Argentina
Fil: Gallo, Carola. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono; Argentina
description A conformationally restricted 2-O-benzyl-3,5-O-di-tert-butylsilylene-b-D-thiogalactofuranoside donor was prepared from benzyl alpha-D-galactofuranoside and its donor capability was studied for stereoselective 1,2-cis a-D-galactofuranosylation. An unusual chemical behavior on benzylation and hydrogenolysis reactions was observed after the introduction of the 3,5-O-di-tert-butylsilylene protecting group into the galactofuranosyl moiety. The influence of the solvent, temperature and activating system was evaluated. The NIS/AgOTf system, widely used in 1,2-cis b-arabinofuranosylation, was not satisfactory enough for 1,2-cis galactofuranosylation. However, moderate to high alpha-selectivity was obtained with all the acceptors employed when used p-NO2PhSCl/AgOTf as a promoting system, in CH2Cl2 at -78 ºC. The order of the addition of the reactants (premixing or preactivation) did not affect substantially the stereochemical course of the glycosylation reaction. The a-D-Galf-(1-6)-D-Man linkage was achieved with complete diastereoselectivity by preactivation of the conformationally constrained thioglycoside donor.
publishDate 2014
dc.date.none.fl_str_mv 2014-08
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/11336/8158
Tilve, Mariano Javier; Gallo, Carola; Conformationally restricted 3,5-O-(di-tert-butylsilylene)-D-galactofuranosyl thioglycoside donor for 1,2-cis a-D-galactofuranosylation; Elsevier; Carbohydrate Research; 397; 8-2014; 7-17
0008-6215
url http://hdl.handle.net/11336/8158
identifier_str_mv Tilve, Mariano Javier; Gallo, Carola; Conformationally restricted 3,5-O-(di-tert-butylsilylene)-D-galactofuranosyl thioglycoside donor for 1,2-cis a-D-galactofuranosylation; Elsevier; Carbohydrate Research; 397; 8-2014; 7-17
0008-6215
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0008621514003085
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.carres.2014.07.024
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv 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 13.22299

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