Conformationally restricted 3,5-O-(di-tert-butylsilylene)-d- galactofuranosyl thioglycoside donor for 1,2-cis α-d-galactofuranosylation
A conformationally restricted 2-O-benzyl-3,5-O-di-tert-butylsilylene- β-d-thiogalactofuranoside donor was prepared from benzyl α-d-galactofuranoside and its donor capability was studied for stereoselective 1,2-cis α-d-galactofuranosylation. An unusual chemical behavior in benzylation and hydrogenoly...
Guardado en:
| Autores principales: | , |
|---|---|
| Formato: | JOUR |
| Materias: | |
| Acceso en línea: | http://hdl.handle.net/20.500.12110/paper_00086215_v397_n_p7_Tilve |
| Aporte de: |
| id |
todo:paper_00086215_v397_n_p7_Tilve |
|---|---|
| record_format |
dspace |
| spelling |
todo:paper_00086215_v397_n_p7_Tilve2023-10-03T14:07:32Z Conformationally restricted 3,5-O-(di-tert-butylsilylene)-d- galactofuranosyl thioglycoside donor for 1,2-cis α-d-galactofuranosylation Tilve, M.J. Gallo-Rodriguez, C. 1,2-cis Galactofuranose Glycosylation Protecting groups Solvents effects Thioglycoside Glycosylation Stereoselectivity 1,2-cis Chemical behavior Diastereo-selectivity Galactofuranose Glycosylation reactions Hydrogenolysis reactions Protecting group Thioglycosides Esterification Glycosylation 4 tolyl 6 o acetyl 2 o benzyl 3,5 o (di tert butylsilanediyl) 1 thiol beta dextro galactofuranoside cyclohexanol solvent thioglycoside unclassified drug 3,5-O-di-tert-butylsilylene-beta-D-thiogalactofuranoside butane di-tert-butylsilylene silane derivative thioglycoside acetylation article benzylation carbon nuclear magnetic resonance chemical modification conformation galactofuranosylation glycosylation hydrogen bond hydrogenolysis nonhuman priority journal proton nuclear magnetic resonance stereochemistry synthesis Talaromyces flavus temperature thin layer chromatography Trypanosoma cruzi chemistry conformation glycosylation stereoisomerism Article carbohydrate synthesis column chromatography controlled study heteronuclear single quantum coherence low temperature nucleophilicity precursor purification Butanes Carbohydrate Conformation Chemistry Techniques, Synthetic Glycosylation Silanes Solvents Stereoisomerism Thiogalactosides Thioglycosides A conformationally restricted 2-O-benzyl-3,5-O-di-tert-butylsilylene- β-d-thiogalactofuranoside donor was prepared from benzyl α-d-galactofuranoside and its donor capability was studied for stereoselective 1,2-cis α-d-galactofuranosylation. An unusual chemical behavior in benzylation and hydrogenolysis reactions was observed after the introduction of the 3,5-O-di-tert-butylsilylene protecting group into the galactofuranosyl moiety. The influence of the solvent, temperature, and activating system was evaluated. The NIS/AgOTf system, widely used in 1,2-cis β-arabinofuranosylation, was not satisfactory enough for 1,2-cis galactofuranosylation. However, moderate to high α-selectivity was obtained with all the acceptors employed when using p-NO2PhSCl/AgOTf as a promoting system, in CH2Cl2 at -78 °C. The order of the addition of the reactants (premixing or preactivation) did not affect substantially the stereochemical course of the glycosylation reaction. The α-d-Galf-(1→6)-d-Man linkage was achieved with complete diastereoselectivity by preactivation of the conformationally constrained thioglycoside donor. © 2014 Elsevier Ltd. All rights reserved. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00086215_v397_n_p7_Tilve |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
1,2-cis Galactofuranose Glycosylation Protecting groups Solvents effects Thioglycoside Glycosylation Stereoselectivity 1,2-cis Chemical behavior Diastereo-selectivity Galactofuranose Glycosylation reactions Hydrogenolysis reactions Protecting group Thioglycosides Esterification Glycosylation 4 tolyl 6 o acetyl 2 o benzyl 3,5 o (di tert butylsilanediyl) 1 thiol beta dextro galactofuranoside cyclohexanol solvent thioglycoside unclassified drug 3,5-O-di-tert-butylsilylene-beta-D-thiogalactofuranoside butane di-tert-butylsilylene silane derivative thioglycoside acetylation article benzylation carbon nuclear magnetic resonance chemical modification conformation galactofuranosylation glycosylation hydrogen bond hydrogenolysis nonhuman priority journal proton nuclear magnetic resonance stereochemistry synthesis Talaromyces flavus temperature thin layer chromatography Trypanosoma cruzi chemistry conformation glycosylation stereoisomerism Article carbohydrate synthesis column chromatography controlled study heteronuclear single quantum coherence low temperature nucleophilicity precursor purification Butanes Carbohydrate Conformation Chemistry Techniques, Synthetic Glycosylation Silanes Solvents Stereoisomerism Thiogalactosides Thioglycosides |
| spellingShingle |
1,2-cis Galactofuranose Glycosylation Protecting groups Solvents effects Thioglycoside Glycosylation Stereoselectivity 1,2-cis Chemical behavior Diastereo-selectivity Galactofuranose Glycosylation reactions Hydrogenolysis reactions Protecting group Thioglycosides Esterification Glycosylation 4 tolyl 6 o acetyl 2 o benzyl 3,5 o (di tert butylsilanediyl) 1 thiol beta dextro galactofuranoside cyclohexanol solvent thioglycoside unclassified drug 3,5-O-di-tert-butylsilylene-beta-D-thiogalactofuranoside butane di-tert-butylsilylene silane derivative thioglycoside acetylation article benzylation carbon nuclear magnetic resonance chemical modification conformation galactofuranosylation glycosylation hydrogen bond hydrogenolysis nonhuman priority journal proton nuclear magnetic resonance stereochemistry synthesis Talaromyces flavus temperature thin layer chromatography Trypanosoma cruzi chemistry conformation glycosylation stereoisomerism Article carbohydrate synthesis column chromatography controlled study heteronuclear single quantum coherence low temperature nucleophilicity precursor purification Butanes Carbohydrate Conformation Chemistry Techniques, Synthetic Glycosylation Silanes Solvents Stereoisomerism Thiogalactosides Thioglycosides Tilve, M.J. Gallo-Rodriguez, C. Conformationally restricted 3,5-O-(di-tert-butylsilylene)-d- galactofuranosyl thioglycoside donor for 1,2-cis α-d-galactofuranosylation |
| topic_facet |
1,2-cis Galactofuranose Glycosylation Protecting groups Solvents effects Thioglycoside Glycosylation Stereoselectivity 1,2-cis Chemical behavior Diastereo-selectivity Galactofuranose Glycosylation reactions Hydrogenolysis reactions Protecting group Thioglycosides Esterification Glycosylation 4 tolyl 6 o acetyl 2 o benzyl 3,5 o (di tert butylsilanediyl) 1 thiol beta dextro galactofuranoside cyclohexanol solvent thioglycoside unclassified drug 3,5-O-di-tert-butylsilylene-beta-D-thiogalactofuranoside butane di-tert-butylsilylene silane derivative thioglycoside acetylation article benzylation carbon nuclear magnetic resonance chemical modification conformation galactofuranosylation glycosylation hydrogen bond hydrogenolysis nonhuman priority journal proton nuclear magnetic resonance stereochemistry synthesis Talaromyces flavus temperature thin layer chromatography Trypanosoma cruzi chemistry conformation glycosylation stereoisomerism Article carbohydrate synthesis column chromatography controlled study heteronuclear single quantum coherence low temperature nucleophilicity precursor purification Butanes Carbohydrate Conformation Chemistry Techniques, Synthetic Glycosylation Silanes Solvents Stereoisomerism Thiogalactosides Thioglycosides |
| description |
A conformationally restricted 2-O-benzyl-3,5-O-di-tert-butylsilylene- β-d-thiogalactofuranoside donor was prepared from benzyl α-d-galactofuranoside and its donor capability was studied for stereoselective 1,2-cis α-d-galactofuranosylation. An unusual chemical behavior in benzylation and hydrogenolysis reactions was observed after the introduction of the 3,5-O-di-tert-butylsilylene protecting group into the galactofuranosyl moiety. The influence of the solvent, temperature, and activating system was evaluated. The NIS/AgOTf system, widely used in 1,2-cis β-arabinofuranosylation, was not satisfactory enough for 1,2-cis galactofuranosylation. However, moderate to high α-selectivity was obtained with all the acceptors employed when using p-NO2PhSCl/AgOTf as a promoting system, in CH2Cl2 at -78 °C. The order of the addition of the reactants (premixing or preactivation) did not affect substantially the stereochemical course of the glycosylation reaction. The α-d-Galf-(1→6)-d-Man linkage was achieved with complete diastereoselectivity by preactivation of the conformationally constrained thioglycoside donor. © 2014 Elsevier Ltd. All rights reserved. |
| format |
JOUR |
| author |
Tilve, M.J. Gallo-Rodriguez, C. |
| author_facet |
Tilve, M.J. Gallo-Rodriguez, C. |
| author_sort |
Tilve, M.J. |
| title |
Conformationally restricted 3,5-O-(di-tert-butylsilylene)-d- galactofuranosyl thioglycoside donor for 1,2-cis α-d-galactofuranosylation |
| title_short |
Conformationally restricted 3,5-O-(di-tert-butylsilylene)-d- galactofuranosyl thioglycoside donor for 1,2-cis α-d-galactofuranosylation |
| title_full |
Conformationally restricted 3,5-O-(di-tert-butylsilylene)-d- galactofuranosyl thioglycoside donor for 1,2-cis α-d-galactofuranosylation |
| title_fullStr |
Conformationally restricted 3,5-O-(di-tert-butylsilylene)-d- galactofuranosyl thioglycoside donor for 1,2-cis α-d-galactofuranosylation |
| title_full_unstemmed |
Conformationally restricted 3,5-O-(di-tert-butylsilylene)-d- galactofuranosyl thioglycoside donor for 1,2-cis α-d-galactofuranosylation |
| title_sort |
conformationally restricted 3,5-o-(di-tert-butylsilylene)-d- galactofuranosyl thioglycoside donor for 1,2-cis α-d-galactofuranosylation |
| url |
http://hdl.handle.net/20.500.12110/paper_00086215_v397_n_p7_Tilve |
| work_keys_str_mv |
AT tilvemj conformationallyrestricted35oditertbutylsilylenedgalactofuranosylthioglycosidedonorfor12cisadgalactofuranosylation AT gallorodriguezc conformationallyrestricted35oditertbutylsilylenedgalactofuranosylthioglycosidedonorfor12cisadgalactofuranosylation |
| _version_ |
1807321845912829952 |