Synthesis of thiodisaccharide sulfoxides and sulfones - Determination of the configuration of the sulfur stereocentre

The oxidation of per-O-acetyl S-(1→3)- and S-(1→4)-linked thiodisaccharides containing glucose, gulose and galactose residues with an excess of m-chloroperbenzoic acid gave the corresponding sulfoxides or sulfones. Sulfones were formed when the oxidation reaction was left for longer times. The sulfo...

Descripción completa

Guardado en:

Detalles Bibliográficos
Autores principales:	Manzano, Verónica Elena, Varela, Oscar José
Publicado:	2013
Materias:	Carbohydrates Configuration determination Glycoconjugates Sulfones Sulfoxides
Acceso en línea:	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1434193X_v_n32_p7343_Colomer http://hdl.handle.net/20.500.12110/paper_1434193X_v_n32_p7343_Colomer
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	paper:paper_1434193X_v_n32_p7343_Colomer
record_format	dspace
spelling	paper:paper_1434193X_v_n32_p7343_Colomer2023-06-08T16:14:25Z Synthesis of thiodisaccharide sulfoxides and sulfones - Determination of the configuration of the sulfur stereocentre Manzano, Verónica Elena Varela, Oscar José Carbohydrates Configuration determination Glycoconjugates Sulfones Sulfoxides The oxidation of per-O-acetyl S-(1→3)- and S-(1→4)-linked thiodisaccharides containing glucose, gulose and galactose residues with an excess of m-chloroperbenzoic acid gave the corresponding sulfoxides or sulfones. Sulfones were formed when the oxidation reaction was left for longer times. The sulfoxides were obtained as diastereomeric mixtures due to the chirality of the sulfur atom. Both diastereoisomers of the S-(1→3)-linked thiodisaccharide sulfoxides were isolated by column chromatography, whereas the S-(1→4)-linked analogues could not be separated. The absolute configuration of the sulfur stereocentre of the sulfoxides was assigned using NMR spectroscopy, taking into account the preferred conformations of the molecules, and the shielding/deshielding of proton signals caused by the anisotropy of the S=O bond and related effects. Most of the thiodisaccharide sulfoxides were successfully O-deacetylated with MeOH/Et3N/H2O, but the sulfones underwent elimination reactions under these conditions. Therefore, the oxidation was performed on unprotected thiodisaccharides, and the corresponding sulfones were obtained in very good yields. Thiodisaccharides with (1→3) or (1→4) linkages, and with glucose or galactose at the non-reducing end, were oxidized with m-chloroperbenzoic acid to give the corresponding sulfoxides or sulfones. The configuration of the sulfur stereocentre of the sulfoxides was assigned using NMR spectroscopy, based on the anisotropy of the S=O bond and related effects. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Fil:Manzano, V.E. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Varela, O. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2013 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1434193X_v_n32_p7343_Colomer http://hdl.handle.net/20.500.12110/paper_1434193X_v_n32_p7343_Colomer
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	Carbohydrates Configuration determination Glycoconjugates Sulfones Sulfoxides
spellingShingle	Carbohydrates Configuration determination Glycoconjugates Sulfones Sulfoxides Manzano, Verónica Elena Varela, Oscar José Synthesis of thiodisaccharide sulfoxides and sulfones - Determination of the configuration of the sulfur stereocentre
topic_facet	Carbohydrates Configuration determination Glycoconjugates Sulfones Sulfoxides
description	The oxidation of per-O-acetyl S-(1→3)- and S-(1→4)-linked thiodisaccharides containing glucose, gulose and galactose residues with an excess of m-chloroperbenzoic acid gave the corresponding sulfoxides or sulfones. Sulfones were formed when the oxidation reaction was left for longer times. The sulfoxides were obtained as diastereomeric mixtures due to the chirality of the sulfur atom. Both diastereoisomers of the S-(1→3)-linked thiodisaccharide sulfoxides were isolated by column chromatography, whereas the S-(1→4)-linked analogues could not be separated. The absolute configuration of the sulfur stereocentre of the sulfoxides was assigned using NMR spectroscopy, taking into account the preferred conformations of the molecules, and the shielding/deshielding of proton signals caused by the anisotropy of the S=O bond and related effects. Most of the thiodisaccharide sulfoxides were successfully O-deacetylated with MeOH/Et3N/H2O, but the sulfones underwent elimination reactions under these conditions. Therefore, the oxidation was performed on unprotected thiodisaccharides, and the corresponding sulfones were obtained in very good yields. Thiodisaccharides with (1→3) or (1→4) linkages, and with glucose or galactose at the non-reducing end, were oxidized with m-chloroperbenzoic acid to give the corresponding sulfoxides or sulfones. The configuration of the sulfur stereocentre of the sulfoxides was assigned using NMR spectroscopy, based on the anisotropy of the S=O bond and related effects. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
author	Manzano, Verónica Elena Varela, Oscar José
author_facet	Manzano, Verónica Elena Varela, Oscar José
author_sort	Manzano, Verónica Elena
title	Synthesis of thiodisaccharide sulfoxides and sulfones - Determination of the configuration of the sulfur stereocentre
title_short	Synthesis of thiodisaccharide sulfoxides and sulfones - Determination of the configuration of the sulfur stereocentre
title_full	Synthesis of thiodisaccharide sulfoxides and sulfones - Determination of the configuration of the sulfur stereocentre
title_fullStr	Synthesis of thiodisaccharide sulfoxides and sulfones - Determination of the configuration of the sulfur stereocentre
title_full_unstemmed	Synthesis of thiodisaccharide sulfoxides and sulfones - Determination of the configuration of the sulfur stereocentre
title_sort	synthesis of thiodisaccharide sulfoxides and sulfones - determination of the configuration of the sulfur stereocentre
publishDate	2013
url	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1434193X_v_n32_p7343_Colomer http://hdl.handle.net/20.500.12110/paper_1434193X_v_n32_p7343_Colomer
work_keys_str_mv	AT manzanoveronicaelena synthesisofthiodisaccharidesulfoxidesandsulfonesdeterminationoftheconfigurationofthesulfurstereocentre AT varelaoscarjose synthesisofthiodisaccharidesulfoxidesandsulfonesdeterminationoftheconfigurationofthesulfurstereocentre
_version_	1768542471210401792

Synthesis of thiodisaccharide sulfoxides and sulfones - Determination of the configuration of the sulfur stereocentre

Ejemplares similares