Internal asymmetric induction by the C-6 substituent on the oxidation reaction of interglycosidic sulfur atom of thiodisaccharides

Autores
Colomer, Juan Pablo; Peñeñory, Alicia Beatriz; Varela, Oscar Jose
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Since the enantio or diastereoselective preparation of sulfoxides is a current challenge, we explore the possibility of inducing diastereoselectivity in the oxidation of the sulfur atom of thiodisaccharides, according to their substitution patterns. Thus, a series of 3-deoxy-4-S-(β-d-glucopyranosyl)-4-thio-β-d-xylo-hexopyranoside derivatives, with different substituents at C-6 (OH, OAc or OTBS) of the reducing end, have been synthesized and treated with m-CPBA for the oxidation of the sulfur atom at C-4, which is vicinal to C-6. The absolute configuration at the sulfur stereocenter of the resulting sulfoxides was established taking into account shielding/deshielding anisotropic effects of the SO bond on the chemical shift of the NMR signals of selected protons, in the most populated syn φ/syn ψ conformation of the thiodisaccharide S-oxides. The OAc and OTBS derivatives afforded diastereomeric mixtures of R and S sulfoxides in a similar ratio (1.4 : 1 and 1.6 : 1, respectively). In contrast, the oxidation of thiodisaccharide with a free hydroxyl group at C-6 was completely diastereoselective in favor of the R sulfoxide. The influence of the thiodisaccharide C-6 substituent on the stereochemical course of the oxidation is discussed.
Fil: Colomer, Juan Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Peñeñory, Alicia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; 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. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina
Materia
Sulfoxides
Diastereoselectivity
Thiodisaccarides
oxidation
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:11336/64338
Acceder
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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Internal asymmetric induction by the C-6 substituent on the oxidation reaction of interglycosidic sulfur atom of thiodisaccharidesColomer, Juan PabloPeñeñory, Alicia BeatrizVarela, Oscar JoseSulfoxidesDiastereoselectivityThiodisaccaridesoxidationhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Since the enantio or diastereoselective preparation of sulfoxides is a current challenge, we explore the possibility of inducing diastereoselectivity in the oxidation of the sulfur atom of thiodisaccharides, according to their substitution patterns. Thus, a series of 3-deoxy-4-S-(β-d-glucopyranosyl)-4-thio-β-d-xylo-hexopyranoside derivatives, with different substituents at C-6 (OH, OAc or OTBS) of the reducing end, have been synthesized and treated with m-CPBA for the oxidation of the sulfur atom at C-4, which is vicinal to C-6. The absolute configuration at the sulfur stereocenter of the resulting sulfoxides was established taking into account shielding/deshielding anisotropic effects of the SO bond on the chemical shift of the NMR signals of selected protons, in the most populated syn φ/syn ψ conformation of the thiodisaccharide S-oxides. The OAc and OTBS derivatives afforded diastereomeric mixtures of R and S sulfoxides in a similar ratio (1.4 : 1 and 1.6 : 1, respectively). In contrast, the oxidation of thiodisaccharide with a free hydroxyl group at C-6 was completely diastereoselective in favor of the R sulfoxide. The influence of the thiodisaccharide C-6 substituent on the stereochemical course of the oxidation is discussed.Fil: Colomer, Juan Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Peñeñory, Alicia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Varela, Oscar Jose. 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. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; ArgentinaRoyal Society of Chemistry2017-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/64338Colomer, Juan Pablo; Peñeñory, Alicia Beatriz; Varela, Oscar Jose; Internal asymmetric induction by the C-6 substituent on the oxidation reaction of interglycosidic sulfur atom of thiodisaccharides; Royal Society of Chemistry; RSC Advances; 7; 70; 9-2017; 44410-444202046-2069CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/C7RA07225Binfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/Content/ArticleLanding/2017/RA/C7RA07225Binfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:11:51Zoai:ri.conicet.gov.ar:11336/64338instacron: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 10:11:51.719CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Internal asymmetric induction by the C-6 substituent on the oxidation reaction of interglycosidic sulfur atom of thiodisaccharides
title Internal asymmetric induction by the C-6 substituent on the oxidation reaction of interglycosidic sulfur atom of thiodisaccharides
spellingShingle Internal asymmetric induction by the C-6 substituent on the oxidation reaction of interglycosidic sulfur atom of thiodisaccharides
Colomer, Juan Pablo
Sulfoxides
Diastereoselectivity
Thiodisaccarides
oxidation
title_short Internal asymmetric induction by the C-6 substituent on the oxidation reaction of interglycosidic sulfur atom of thiodisaccharides
title_full Internal asymmetric induction by the C-6 substituent on the oxidation reaction of interglycosidic sulfur atom of thiodisaccharides
title_fullStr Internal asymmetric induction by the C-6 substituent on the oxidation reaction of interglycosidic sulfur atom of thiodisaccharides
title_full_unstemmed Internal asymmetric induction by the C-6 substituent on the oxidation reaction of interglycosidic sulfur atom of thiodisaccharides
title_sort Internal asymmetric induction by the C-6 substituent on the oxidation reaction of interglycosidic sulfur atom of thiodisaccharides
dc.creator.none.fl_str_mv Colomer, Juan Pablo
Peñeñory, Alicia Beatriz
Varela, Oscar Jose
author Colomer, Juan Pablo
author_facet Colomer, Juan Pablo
Peñeñory, Alicia Beatriz
Varela, Oscar Jose
author_role author
author2 Peñeñory, Alicia Beatriz
Varela, Oscar Jose
author2_role author
author
dc.subject.none.fl_str_mv Sulfoxides
Diastereoselectivity
Thiodisaccarides
oxidation
topic Sulfoxides
Diastereoselectivity
Thiodisaccarides
oxidation
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Since the enantio or diastereoselective preparation of sulfoxides is a current challenge, we explore the possibility of inducing diastereoselectivity in the oxidation of the sulfur atom of thiodisaccharides, according to their substitution patterns. Thus, a series of 3-deoxy-4-S-(β-d-glucopyranosyl)-4-thio-β-d-xylo-hexopyranoside derivatives, with different substituents at C-6 (OH, OAc or OTBS) of the reducing end, have been synthesized and treated with m-CPBA for the oxidation of the sulfur atom at C-4, which is vicinal to C-6. The absolute configuration at the sulfur stereocenter of the resulting sulfoxides was established taking into account shielding/deshielding anisotropic effects of the SO bond on the chemical shift of the NMR signals of selected protons, in the most populated syn φ/syn ψ conformation of the thiodisaccharide S-oxides. The OAc and OTBS derivatives afforded diastereomeric mixtures of R and S sulfoxides in a similar ratio (1.4 : 1 and 1.6 : 1, respectively). In contrast, the oxidation of thiodisaccharide with a free hydroxyl group at C-6 was completely diastereoselective in favor of the R sulfoxide. The influence of the thiodisaccharide C-6 substituent on the stereochemical course of the oxidation is discussed.
Fil: Colomer, Juan Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Peñeñory, Alicia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; 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. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina
description Since the enantio or diastereoselective preparation of sulfoxides is a current challenge, we explore the possibility of inducing diastereoselectivity in the oxidation of the sulfur atom of thiodisaccharides, according to their substitution patterns. Thus, a series of 3-deoxy-4-S-(β-d-glucopyranosyl)-4-thio-β-d-xylo-hexopyranoside derivatives, with different substituents at C-6 (OH, OAc or OTBS) of the reducing end, have been synthesized and treated with m-CPBA for the oxidation of the sulfur atom at C-4, which is vicinal to C-6. The absolute configuration at the sulfur stereocenter of the resulting sulfoxides was established taking into account shielding/deshielding anisotropic effects of the SO bond on the chemical shift of the NMR signals of selected protons, in the most populated syn φ/syn ψ conformation of the thiodisaccharide S-oxides. The OAc and OTBS derivatives afforded diastereomeric mixtures of R and S sulfoxides in a similar ratio (1.4 : 1 and 1.6 : 1, respectively). In contrast, the oxidation of thiodisaccharide with a free hydroxyl group at C-6 was completely diastereoselective in favor of the R sulfoxide. The influence of the thiodisaccharide C-6 substituent on the stereochemical course of the oxidation is discussed.
publishDate 2017
dc.date.none.fl_str_mv 2017-09
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/11336/64338
Colomer, Juan Pablo; Peñeñory, Alicia Beatriz; Varela, Oscar Jose; Internal asymmetric induction by the C-6 substituent on the oxidation reaction of interglycosidic sulfur atom of thiodisaccharides; Royal Society of Chemistry; RSC Advances; 7; 70; 9-2017; 44410-44420
2046-2069
CONICET Digital
CONICET
url http://hdl.handle.net/11336/64338
identifier_str_mv Colomer, Juan Pablo; Peñeñory, Alicia Beatriz; Varela, Oscar Jose; Internal asymmetric induction by the C-6 substituent on the oxidation reaction of interglycosidic sulfur atom of thiodisaccharides; Royal Society of Chemistry; RSC Advances; 7; 70; 9-2017; 44410-44420
2046-2069
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/C7RA07225B
info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/Content/ArticleLanding/2017/RA/C7RA07225B
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 Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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 12.885934

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