Synthesis of branched dithiotrisaccharides via ring-opening reaction of sugar thiiranes
Satisfactory procedures are described for the synthesis of 5,6- and 3,4-thiirane derivatives from the respective hexofuranose or hexopyranose epoxide precursors. The controlled ring-opening reaction of thiiranes by 1-thioaldoses was successfully accomplished to afford, regio- and stereoselectively,...
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2012
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v77_n1_p253_Repetto http://hdl.handle.net/20.500.12110/paper_00223263_v77_n1_p253_Repetto |
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paper:paper_00223263_v77_n1_p253_Repetto2023-06-08T14:49:36Z Synthesis of branched dithiotrisaccharides via ring-opening reaction of sugar thiiranes Repetto, Evangelina Manzano, Verónica Elena Uhrig, María Laura Varela, Oscar José Cellobiose Crude mixtures Free thiol group Glycosyl donors Good yield Natural polysaccharide Oxidative dimerization Regio-selective Ring opening reaction Stereo-selective Sulfur analogues Thiiranes Trichloroacetimidates Acetylation Sugars Sulfur Synthesis (chemical) 3,4 thiirane derivative 5,6 thiirane derivative carbohydrate derivative cellobiose dithiotrisaccharide lactose trichloroacetimidic acid unclassified drug acetylation article deacetylation dimerization glycosylation ring opening stereochemistry synthesis Carbohydrate Conformation Carbohydrate Sequence Disaccharides Glucose Glycosylation Stereoisomerism Sulfides Trisaccharides Satisfactory procedures are described for the synthesis of 5,6- and 3,4-thiirane derivatives from the respective hexofuranose or hexopyranose epoxide precursors. The controlled ring-opening reaction of thiiranes by 1-thioaldoses was successfully accomplished to afford, regio- and stereoselectively, β-S-(1→4)-3,4-dithiodisaccharides. For instance, the regioselective attack of per-O-acetyl-1-thioglucose (16) to C-4 of 2-propyl 2,6-di-O-acetyl-3,4-epithio-α-d-galactopyranoside (14) gave the derivative of Glcp-β-S-(1→4)-3,4-dithioGlcp-O-iPr (17). This thiodisaccharide was accompanied by the (1→3)-disulfide 18, formed between 16 and 17, and the symmetric (3→3)-disulfide 19, which resulted from the oxidative dimerization of 17. However, the S-acetyl derivative of 17 could be obtained in good yield (62%) by LiAlH 4 reduction of the crude mixture 17-19, followed by acetylation. The same sequence of reactions starting from 14 and the 1-thiolate of Galp afforded the per-O,S-acetyl derivative of Galp-β-S-(1→4)-3,4-dithio-α-d-Glcp-O-iPr (23), which was selectively S-deacetylated to give 25. The dithiosaccharides 17 and 25 are 3,4-di-S-analogues of derivatives of the natural disaccharides cellobiose and lactose, respectively. The ring-opening reaction of 5,6-epithiohexofuranoses of d-galacto (8) or l-altro (11) configuration with 1-thioaldoses was also regio- and stereoselective to give the respective β-S-(1→6)-linked 5,6-dithiodisaccharides 26 or 29 in excellent yields. Glycosylation of the free thiol group of 17, 25, or 26, using trichloroacetimidates as glycosyl donors, led to the corresponding branched dithiotrisaccharides. Some of them are sulfur analogues of derivatives of branched trisaccharides found in natural polysaccharides. © 2011 American Chemical Society. Fil:Repetto, E. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Manzano, V.E. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 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. 2012 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v77_n1_p253_Repetto http://hdl.handle.net/20.500.12110/paper_00223263_v77_n1_p253_Repetto |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Cellobiose Crude mixtures Free thiol group Glycosyl donors Good yield Natural polysaccharide Oxidative dimerization Regio-selective Ring opening reaction Stereo-selective Sulfur analogues Thiiranes Trichloroacetimidates Acetylation Sugars Sulfur Synthesis (chemical) 3,4 thiirane derivative 5,6 thiirane derivative carbohydrate derivative cellobiose dithiotrisaccharide lactose trichloroacetimidic acid unclassified drug acetylation article deacetylation dimerization glycosylation ring opening stereochemistry synthesis Carbohydrate Conformation Carbohydrate Sequence Disaccharides Glucose Glycosylation Stereoisomerism Sulfides Trisaccharides |
| spellingShingle |
Cellobiose Crude mixtures Free thiol group Glycosyl donors Good yield Natural polysaccharide Oxidative dimerization Regio-selective Ring opening reaction Stereo-selective Sulfur analogues Thiiranes Trichloroacetimidates Acetylation Sugars Sulfur Synthesis (chemical) 3,4 thiirane derivative 5,6 thiirane derivative carbohydrate derivative cellobiose dithiotrisaccharide lactose trichloroacetimidic acid unclassified drug acetylation article deacetylation dimerization glycosylation ring opening stereochemistry synthesis Carbohydrate Conformation Carbohydrate Sequence Disaccharides Glucose Glycosylation Stereoisomerism Sulfides Trisaccharides Repetto, Evangelina Manzano, Verónica Elena Uhrig, María Laura Varela, Oscar José Synthesis of branched dithiotrisaccharides via ring-opening reaction of sugar thiiranes |
| topic_facet |
Cellobiose Crude mixtures Free thiol group Glycosyl donors Good yield Natural polysaccharide Oxidative dimerization Regio-selective Ring opening reaction Stereo-selective Sulfur analogues Thiiranes Trichloroacetimidates Acetylation Sugars Sulfur Synthesis (chemical) 3,4 thiirane derivative 5,6 thiirane derivative carbohydrate derivative cellobiose dithiotrisaccharide lactose trichloroacetimidic acid unclassified drug acetylation article deacetylation dimerization glycosylation ring opening stereochemistry synthesis Carbohydrate Conformation Carbohydrate Sequence Disaccharides Glucose Glycosylation Stereoisomerism Sulfides Trisaccharides |
| description |
Satisfactory procedures are described for the synthesis of 5,6- and 3,4-thiirane derivatives from the respective hexofuranose or hexopyranose epoxide precursors. The controlled ring-opening reaction of thiiranes by 1-thioaldoses was successfully accomplished to afford, regio- and stereoselectively, β-S-(1→4)-3,4-dithiodisaccharides. For instance, the regioselective attack of per-O-acetyl-1-thioglucose (16) to C-4 of 2-propyl 2,6-di-O-acetyl-3,4-epithio-α-d-galactopyranoside (14) gave the derivative of Glcp-β-S-(1→4)-3,4-dithioGlcp-O-iPr (17). This thiodisaccharide was accompanied by the (1→3)-disulfide 18, formed between 16 and 17, and the symmetric (3→3)-disulfide 19, which resulted from the oxidative dimerization of 17. However, the S-acetyl derivative of 17 could be obtained in good yield (62%) by LiAlH 4 reduction of the crude mixture 17-19, followed by acetylation. The same sequence of reactions starting from 14 and the 1-thiolate of Galp afforded the per-O,S-acetyl derivative of Galp-β-S-(1→4)-3,4-dithio-α-d-Glcp-O-iPr (23), which was selectively S-deacetylated to give 25. The dithiosaccharides 17 and 25 are 3,4-di-S-analogues of derivatives of the natural disaccharides cellobiose and lactose, respectively. The ring-opening reaction of 5,6-epithiohexofuranoses of d-galacto (8) or l-altro (11) configuration with 1-thioaldoses was also regio- and stereoselective to give the respective β-S-(1→6)-linked 5,6-dithiodisaccharides 26 or 29 in excellent yields. Glycosylation of the free thiol group of 17, 25, or 26, using trichloroacetimidates as glycosyl donors, led to the corresponding branched dithiotrisaccharides. Some of them are sulfur analogues of derivatives of branched trisaccharides found in natural polysaccharides. © 2011 American Chemical Society. |
| author |
Repetto, Evangelina Manzano, Verónica Elena Uhrig, María Laura Varela, Oscar José |
| author_facet |
Repetto, Evangelina Manzano, Verónica Elena Uhrig, María Laura Varela, Oscar José |
| author_sort |
Repetto, Evangelina |
| title |
Synthesis of branched dithiotrisaccharides via ring-opening reaction of sugar thiiranes |
| title_short |
Synthesis of branched dithiotrisaccharides via ring-opening reaction of sugar thiiranes |
| title_full |
Synthesis of branched dithiotrisaccharides via ring-opening reaction of sugar thiiranes |
| title_fullStr |
Synthesis of branched dithiotrisaccharides via ring-opening reaction of sugar thiiranes |
| title_full_unstemmed |
Synthesis of branched dithiotrisaccharides via ring-opening reaction of sugar thiiranes |
| title_sort |
synthesis of branched dithiotrisaccharides via ring-opening reaction of sugar thiiranes |
| publishDate |
2012 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v77_n1_p253_Repetto http://hdl.handle.net/20.500.12110/paper_00223263_v77_n1_p253_Repetto |
| work_keys_str_mv |
AT repettoevangelina synthesisofbrancheddithiotrisaccharidesviaringopeningreactionofsugarthiiranes AT manzanoveronicaelena synthesisofbrancheddithiotrisaccharidesviaringopeningreactionofsugarthiiranes AT uhrigmarialaura synthesisofbrancheddithiotrisaccharidesviaringopeningreactionofsugarthiiranes AT varelaoscarjose synthesisofbrancheddithiotrisaccharidesviaringopeningreactionofsugarthiiranes |
| _version_ |
1768546334059528192 |