Conformational behavior of peracetylated β-d-mannopyranosyl methanesulfonamide: implications for the mechanism of sulfonamidoglycosylation of carbohydrate derivatives

Autores
Lavecchia, Martín José; Rodríguez, Oscar Mariano; Echeverría, Gustavo Alberto; Pis Diez, Reinaldo; Colinas, Pedro Alfonso
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The conformational behavior of 2,3,4,6-tetra-O-acetyl-b-D-mannopyranosyl methanesulfonamide has been investigated from a combined theoretical and experimental point of view. The study of the conformational space of the glycosyl sulfonamide revealed that the b anomer is thermodynamically more stable than the a one. This fact suggests that the synthesis reaction could take place mainly under thermodynamic control as the main experimental product is the b-anomeric form of the sulfonamide. Several intramolecular hydrogen bonds were found in the stable conformers of the N-mannopyranosyl sulfonamide under study. A relationship was found to exist between them and the relative stability of the conformers. A detailed analysis of geometrical parameters shed light into the nature of the solid state structure of the novel 2,3,4,6-tetra-O-acetyl-b-D-mannopyranosyl methanesulfonamide in terms of exo- and endo-anomeric effects and antiperiplanar relationships. NBO calculations confirmed those findings. Calculated 1 H and 13C NMR chemical shifts support previous findings concerning configuration and conformation assignments of the title sulfonamide. Finally, an explanation of the stereochemical outcome of sulfonamidoglycosylations, was given in terms of exo- and endo-anomeric effects and steric factors.
Fil: Lavecchia, Martín José. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Rodríguez, Oscar Mariano. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina
Fil: Echeverría, Gustavo Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; Argentina
Fil: Pis Diez, Reinaldo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Colinas, Pedro Alfonso. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; Argentina
Materia
Glycosyl sulfonamides
Sulfonamidoglycosylation
endo-Anomeric effect
exo-Anomeric effect
Density functional theory
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:11336/270857
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/270857
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Conformational behavior of peracetylated β-d-mannopyranosyl methanesulfonamide: implications for the mechanism of sulfonamidoglycosylation of carbohydrate derivativesLavecchia, Martín JoséRodríguez, Oscar MarianoEcheverría, Gustavo AlbertoPis Diez, ReinaldoColinas, Pedro AlfonsoGlycosyl sulfonamidesSulfonamidoglycosylationendo-Anomeric effectexo-Anomeric effectDensity functional theoryhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The conformational behavior of 2,3,4,6-tetra-O-acetyl-b-D-mannopyranosyl methanesulfonamide has been investigated from a combined theoretical and experimental point of view. The study of the conformational space of the glycosyl sulfonamide revealed that the b anomer is thermodynamically more stable than the a one. This fact suggests that the synthesis reaction could take place mainly under thermodynamic control as the main experimental product is the b-anomeric form of the sulfonamide. Several intramolecular hydrogen bonds were found in the stable conformers of the N-mannopyranosyl sulfonamide under study. A relationship was found to exist between them and the relative stability of the conformers. A detailed analysis of geometrical parameters shed light into the nature of the solid state structure of the novel 2,3,4,6-tetra-O-acetyl-b-D-mannopyranosyl methanesulfonamide in terms of exo- and endo-anomeric effects and antiperiplanar relationships. NBO calculations confirmed those findings. Calculated 1 H and 13C NMR chemical shifts support previous findings concerning configuration and conformation assignments of the title sulfonamide. Finally, an explanation of the stereochemical outcome of sulfonamidoglycosylations, was given in terms of exo- and endo-anomeric effects and steric factors.Fil: Lavecchia, Martín José. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Rodríguez, Oscar Mariano. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; ArgentinaFil: Echeverría, Gustavo Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; ArgentinaFil: Pis Diez, Reinaldo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Colinas, Pedro Alfonso. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; ArgentinaElsevier2012-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/270857Lavecchia, Martín José; Rodríguez, Oscar Mariano; Echeverría, Gustavo Alberto; Pis Diez, Reinaldo; Colinas, Pedro Alfonso; Conformational behavior of peracetylated β-d-mannopyranosyl methanesulfonamide: implications for the mechanism of sulfonamidoglycosylation of carbohydrate derivatives; Elsevier; Carbohydrate Research; 361; 11-2012; 182-1880008-6215CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S0008621512003631info:eu-repo/semantics/altIdentifier/doi/10.1016/j.carres.2012.08.016info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:35:13Zoai:ri.conicet.gov.ar:11336/270857instacron: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 14:35:14.106CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Conformational behavior of peracetylated β-d-mannopyranosyl methanesulfonamide: implications for the mechanism of sulfonamidoglycosylation of carbohydrate derivatives
title Conformational behavior of peracetylated β-d-mannopyranosyl methanesulfonamide: implications for the mechanism of sulfonamidoglycosylation of carbohydrate derivatives
spellingShingle Conformational behavior of peracetylated β-d-mannopyranosyl methanesulfonamide: implications for the mechanism of sulfonamidoglycosylation of carbohydrate derivatives
Lavecchia, Martín José
Glycosyl sulfonamides
Sulfonamidoglycosylation
endo-Anomeric effect
exo-Anomeric effect
Density functional theory
title_short Conformational behavior of peracetylated β-d-mannopyranosyl methanesulfonamide: implications for the mechanism of sulfonamidoglycosylation of carbohydrate derivatives
title_full Conformational behavior of peracetylated β-d-mannopyranosyl methanesulfonamide: implications for the mechanism of sulfonamidoglycosylation of carbohydrate derivatives
title_fullStr Conformational behavior of peracetylated β-d-mannopyranosyl methanesulfonamide: implications for the mechanism of sulfonamidoglycosylation of carbohydrate derivatives
title_full_unstemmed Conformational behavior of peracetylated β-d-mannopyranosyl methanesulfonamide: implications for the mechanism of sulfonamidoglycosylation of carbohydrate derivatives
title_sort Conformational behavior of peracetylated β-d-mannopyranosyl methanesulfonamide: implications for the mechanism of sulfonamidoglycosylation of carbohydrate derivatives
dc.creator.none.fl_str_mv Lavecchia, Martín José
Rodríguez, Oscar Mariano
Echeverría, Gustavo Alberto
Pis Diez, Reinaldo
Colinas, Pedro Alfonso
author Lavecchia, Martín José
author_facet Lavecchia, Martín José
Rodríguez, Oscar Mariano
Echeverría, Gustavo Alberto
Pis Diez, Reinaldo
Colinas, Pedro Alfonso
author_role author
author2 Rodríguez, Oscar Mariano
Echeverría, Gustavo Alberto
Pis Diez, Reinaldo
Colinas, Pedro Alfonso
author2_role author
author
author
author
dc.subject.none.fl_str_mv Glycosyl sulfonamides
Sulfonamidoglycosylation
endo-Anomeric effect
exo-Anomeric effect
Density functional theory
topic Glycosyl sulfonamides
Sulfonamidoglycosylation
endo-Anomeric effect
exo-Anomeric effect
Density functional theory
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 conformational behavior of 2,3,4,6-tetra-O-acetyl-b-D-mannopyranosyl methanesulfonamide has been investigated from a combined theoretical and experimental point of view. The study of the conformational space of the glycosyl sulfonamide revealed that the b anomer is thermodynamically more stable than the a one. This fact suggests that the synthesis reaction could take place mainly under thermodynamic control as the main experimental product is the b-anomeric form of the sulfonamide. Several intramolecular hydrogen bonds were found in the stable conformers of the N-mannopyranosyl sulfonamide under study. A relationship was found to exist between them and the relative stability of the conformers. A detailed analysis of geometrical parameters shed light into the nature of the solid state structure of the novel 2,3,4,6-tetra-O-acetyl-b-D-mannopyranosyl methanesulfonamide in terms of exo- and endo-anomeric effects and antiperiplanar relationships. NBO calculations confirmed those findings. Calculated 1 H and 13C NMR chemical shifts support previous findings concerning configuration and conformation assignments of the title sulfonamide. Finally, an explanation of the stereochemical outcome of sulfonamidoglycosylations, was given in terms of exo- and endo-anomeric effects and steric factors.
Fil: Lavecchia, Martín José. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Rodríguez, Oscar Mariano. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina
Fil: Echeverría, Gustavo Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; Argentina
Fil: Pis Diez, Reinaldo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Colinas, Pedro Alfonso. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; Argentina
description The conformational behavior of 2,3,4,6-tetra-O-acetyl-b-D-mannopyranosyl methanesulfonamide has been investigated from a combined theoretical and experimental point of view. The study of the conformational space of the glycosyl sulfonamide revealed that the b anomer is thermodynamically more stable than the a one. This fact suggests that the synthesis reaction could take place mainly under thermodynamic control as the main experimental product is the b-anomeric form of the sulfonamide. Several intramolecular hydrogen bonds were found in the stable conformers of the N-mannopyranosyl sulfonamide under study. A relationship was found to exist between them and the relative stability of the conformers. A detailed analysis of geometrical parameters shed light into the nature of the solid state structure of the novel 2,3,4,6-tetra-O-acetyl-b-D-mannopyranosyl methanesulfonamide in terms of exo- and endo-anomeric effects and antiperiplanar relationships. NBO calculations confirmed those findings. Calculated 1 H and 13C NMR chemical shifts support previous findings concerning configuration and conformation assignments of the title sulfonamide. Finally, an explanation of the stereochemical outcome of sulfonamidoglycosylations, was given in terms of exo- and endo-anomeric effects and steric factors.
publishDate 2012
dc.date.none.fl_str_mv 2012-11
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/11336/270857
Lavecchia, Martín José; Rodríguez, Oscar Mariano; Echeverría, Gustavo Alberto; Pis Diez, Reinaldo; Colinas, Pedro Alfonso; Conformational behavior of peracetylated β-d-mannopyranosyl methanesulfonamide: implications for the mechanism of sulfonamidoglycosylation of carbohydrate derivatives; Elsevier; Carbohydrate Research; 361; 11-2012; 182-188
0008-6215
CONICET Digital
CONICET
url http://hdl.handle.net/11336/270857
identifier_str_mv Lavecchia, Martín José; Rodríguez, Oscar Mariano; Echeverría, Gustavo Alberto; Pis Diez, Reinaldo; Colinas, Pedro Alfonso; Conformational behavior of peracetylated β-d-mannopyranosyl methanesulfonamide: implications for the mechanism of sulfonamidoglycosylation of carbohydrate derivatives; Elsevier; Carbohydrate Research; 361; 11-2012; 182-188
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/abs/pii/S0008621512003631
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.carres.2012.08.016
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
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 13.22299

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