Synthesis of non-glycosidic 4,6′-thioether-linked disaccharides as hydrolytically stable glycomimetics

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Michael addition of 1,2:3,4-di-O-isopropylidene-6-thio-α-d-galactose (2) to 2-propyl 6-O-acetyl-3,4-dideoxy-α-d-glycero-hex-3-enopyranosid-2-ulose (1) afforded, as the major diastereoisomer, 2-propyl 6-O-acetyl-3-deoxy-4-S-(6-deoxy-1,2:3,4-di-O-isopropylidene-α-d-ga lactopyranos-6-yl)-4-thio-α-d-thr...

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Autores principales:	Uhrig, M.L., Szilágyi, L., Kövér, K.E., Varela, O.
Formato:	JOUR
Materias:	4,6′-Thioether-linked sugars Michael addition Sugar enones Thioether-linked disaccharide analogues Acid hydrolysis Diastereoisomer Disaccharides Glycomimetics Acetylation Addition reactions Chemical bonds Chemical stability Hydrolysis Synthesis (chemical) Sugars 2 propyl 3 deoxy 4 s (methyl 6 deoxy alpha dextro glucopyranos 6 yl) 4 thio alpha dextro xylo hexopyranoside 3 deoxy 4 thiohexopyranose carbonyl derivative disaccharide methyl 2,3,4 tri o benzoyl 6 thio alpha dextro glycopyranoside pyran derivative pyranoside unclassified drug article chemical modification deacetylation hydrolysis priority journal stereochemistry synthesis Carbohydrate Conformation Glycosides Hypoglycemic Agents Models, Molecular Sulfides
Acceso en línea:	http://hdl.handle.net/20.500.12110/paper_00086215_v342_n12-13_p1841_Uhrig
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

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spelling	todo:paper_00086215_v342_n12-13_p1841_Uhrig2023-10-03T14:07:15Z Synthesis of non-glycosidic 4,6′-thioether-linked disaccharides as hydrolytically stable glycomimetics Uhrig, M.L. Szilágyi, L. Kövér, K.E. Varela, O. 4,6′-Thioether-linked sugars Michael addition Sugar enones Thioether-linked disaccharide analogues Acid hydrolysis Diastereoisomer Disaccharides Glycomimetics Michael addition Acetylation Addition reactions Chemical bonds Chemical stability Hydrolysis Synthesis (chemical) Sugars 2 propyl 3 deoxy 4 s (methyl 6 deoxy alpha dextro glucopyranos 6 yl) 4 thio alpha dextro xylo hexopyranoside 3 deoxy 4 thiohexopyranose carbonyl derivative disaccharide methyl 2,3,4 tri o benzoyl 6 thio alpha dextro glycopyranoside pyran derivative pyranoside unclassified drug article chemical modification deacetylation hydrolysis Michael addition priority journal stereochemistry synthesis Carbohydrate Conformation Disaccharides Glycosides Hypoglycemic Agents Models, Molecular Sulfides Michael addition of 1,2:3,4-di-O-isopropylidene-6-thio-α-d-galactose (2) to 2-propyl 6-O-acetyl-3,4-dideoxy-α-d-glycero-hex-3-enopyranosid-2-ulose (1) afforded, as the major diastereoisomer, 2-propyl 6-O-acetyl-3-deoxy-4-S-(6-deoxy-1,2:3,4-di-O-isopropylidene-α-d-ga lactopyranos-6-yl)-4-thio-α-d-threo-hexopyranosid-2-ulose (3, 91% yield). Reduction of the carbonyl group of 3, followed by O-deacetylation gave the two epimers 7 (α-d-lyxo) and 8 (α-d-xylo) in a 1:2 ratio. On removal of the protecting groups of 8 by acid hydrolysis, formation of an 1,6-anhydro bridge was observed in the 3-deoxy-4-thiohexopyranose unit (10). The free non-glycosidic thioether-linked disaccharide 3-deoxy-4-S-(6-deoxy-α,β-d-galactopyranos-6-yl)-4-thio- α,β-d-xylo-hexopyranose (11) was obtained by acetolysis of 10 followed by O-deacetylation. A similar sequence starting from the enone 1 and methyl 2,3,4-tri-O-benzoyl-6-thio-α-d-glucopyranoside (12) led successfully to 2-propyl 3-deoxy-4-S-(methyl 6-deoxy-α-d-glucopyranos-6-yl)-4-thio-α-d-lyxo-hexopyranosid e (17) and its α-d-xylo analog (19, major product). In this synthetic route, orthogonal sets of protecting groups were employed to preserve the configuration of both reducing ends and to avoid the formation of the 1,6-anhydro ring. © 2007 Elsevier Ltd. All rights reserved. Fil:Uhrig, M.L. 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. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00086215_v342_n12-13_p1841_Uhrig
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	4,6′-Thioether-linked sugars Michael addition Sugar enones Thioether-linked disaccharide analogues Acid hydrolysis Diastereoisomer Disaccharides Glycomimetics Michael addition Acetylation Addition reactions Chemical bonds Chemical stability Hydrolysis Synthesis (chemical) Sugars 2 propyl 3 deoxy 4 s (methyl 6 deoxy alpha dextro glucopyranos 6 yl) 4 thio alpha dextro xylo hexopyranoside 3 deoxy 4 thiohexopyranose carbonyl derivative disaccharide methyl 2,3,4 tri o benzoyl 6 thio alpha dextro glycopyranoside pyran derivative pyranoside unclassified drug article chemical modification deacetylation hydrolysis Michael addition priority journal stereochemistry synthesis Carbohydrate Conformation Disaccharides Glycosides Hypoglycemic Agents Models, Molecular Sulfides
spellingShingle	4,6′-Thioether-linked sugars Michael addition Sugar enones Thioether-linked disaccharide analogues Acid hydrolysis Diastereoisomer Disaccharides Glycomimetics Michael addition Acetylation Addition reactions Chemical bonds Chemical stability Hydrolysis Synthesis (chemical) Sugars 2 propyl 3 deoxy 4 s (methyl 6 deoxy alpha dextro glucopyranos 6 yl) 4 thio alpha dextro xylo hexopyranoside 3 deoxy 4 thiohexopyranose carbonyl derivative disaccharide methyl 2,3,4 tri o benzoyl 6 thio alpha dextro glycopyranoside pyran derivative pyranoside unclassified drug article chemical modification deacetylation hydrolysis Michael addition priority journal stereochemistry synthesis Carbohydrate Conformation Disaccharides Glycosides Hypoglycemic Agents Models, Molecular Sulfides Uhrig, M.L. Szilágyi, L. Kövér, K.E. Varela, O. Synthesis of non-glycosidic 4,6′-thioether-linked disaccharides as hydrolytically stable glycomimetics
topic_facet	4,6′-Thioether-linked sugars Michael addition Sugar enones Thioether-linked disaccharide analogues Acid hydrolysis Diastereoisomer Disaccharides Glycomimetics Michael addition Acetylation Addition reactions Chemical bonds Chemical stability Hydrolysis Synthesis (chemical) Sugars 2 propyl 3 deoxy 4 s (methyl 6 deoxy alpha dextro glucopyranos 6 yl) 4 thio alpha dextro xylo hexopyranoside 3 deoxy 4 thiohexopyranose carbonyl derivative disaccharide methyl 2,3,4 tri o benzoyl 6 thio alpha dextro glycopyranoside pyran derivative pyranoside unclassified drug article chemical modification deacetylation hydrolysis Michael addition priority journal stereochemistry synthesis Carbohydrate Conformation Disaccharides Glycosides Hypoglycemic Agents Models, Molecular Sulfides
description	Michael addition of 1,2:3,4-di-O-isopropylidene-6-thio-α-d-galactose (2) to 2-propyl 6-O-acetyl-3,4-dideoxy-α-d-glycero-hex-3-enopyranosid-2-ulose (1) afforded, as the major diastereoisomer, 2-propyl 6-O-acetyl-3-deoxy-4-S-(6-deoxy-1,2:3,4-di-O-isopropylidene-α-d-ga lactopyranos-6-yl)-4-thio-α-d-threo-hexopyranosid-2-ulose (3, 91% yield). Reduction of the carbonyl group of 3, followed by O-deacetylation gave the two epimers 7 (α-d-lyxo) and 8 (α-d-xylo) in a 1:2 ratio. On removal of the protecting groups of 8 by acid hydrolysis, formation of an 1,6-anhydro bridge was observed in the 3-deoxy-4-thiohexopyranose unit (10). The free non-glycosidic thioether-linked disaccharide 3-deoxy-4-S-(6-deoxy-α,β-d-galactopyranos-6-yl)-4-thio- α,β-d-xylo-hexopyranose (11) was obtained by acetolysis of 10 followed by O-deacetylation. A similar sequence starting from the enone 1 and methyl 2,3,4-tri-O-benzoyl-6-thio-α-d-glucopyranoside (12) led successfully to 2-propyl 3-deoxy-4-S-(methyl 6-deoxy-α-d-glucopyranos-6-yl)-4-thio-α-d-lyxo-hexopyranosid e (17) and its α-d-xylo analog (19, major product). In this synthetic route, orthogonal sets of protecting groups were employed to preserve the configuration of both reducing ends and to avoid the formation of the 1,6-anhydro ring. © 2007 Elsevier Ltd. All rights reserved.
format	JOUR
author	Uhrig, M.L. Szilágyi, L. Kövér, K.E. Varela, O.
author_facet	Uhrig, M.L. Szilágyi, L. Kövér, K.E. Varela, O.
author_sort	Uhrig, M.L.
title	Synthesis of non-glycosidic 4,6′-thioether-linked disaccharides as hydrolytically stable glycomimetics
title_short	Synthesis of non-glycosidic 4,6′-thioether-linked disaccharides as hydrolytically stable glycomimetics
title_full	Synthesis of non-glycosidic 4,6′-thioether-linked disaccharides as hydrolytically stable glycomimetics
title_fullStr	Synthesis of non-glycosidic 4,6′-thioether-linked disaccharides as hydrolytically stable glycomimetics
title_full_unstemmed	Synthesis of non-glycosidic 4,6′-thioether-linked disaccharides as hydrolytically stable glycomimetics
title_sort	synthesis of non-glycosidic 4,6′-thioether-linked disaccharides as hydrolytically stable glycomimetics
url	http://hdl.handle.net/20.500.12110/paper_00086215_v342_n12-13_p1841_Uhrig
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_version_	1807322091023761408

Synthesis of non-glycosidic 4,6′-thioether-linked disaccharides as hydrolytically stable glycomimetics

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