Regioselective 5-O-Opening of Conformationally Locked 3,5-O-Di-tert-butylsilylene- d -galactofuranosides. Synthesis of (1→5)-β- d -Galactofuranosyl Derivatives
The use of thiogalactofuranoside as donors for the construction of internal Galf containing oligosaccharide is limited, probably due to the difficulty to functionalize thiogalactofuranoside derivatives showing O-2, O-3, and O-5 with similar reactivity. An efficient method for complete regioselective...
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todo:paper_00223263_v81_n20_p9585_Tilve2023-10-03T14:31:31Z Regioselective 5-O-Opening of Conformationally Locked 3,5-O-Di-tert-butylsilylene- d -galactofuranosides. Synthesis of (1→5)-β- d -Galactofuranosyl Derivatives Tilve, M.J. Cori, C.R. Gallo-Rodriguez, C. Oligosaccharides Autocondensation Glycosylation reactions Hydroxyl groups Innovative approaches Regio-selective Thioglycosides Regioselectivity disaccharide furan derivative galactose oligosaccharide hydroxyl group n acetylgalactosamine oligosaccharide thioglycoside trisaccharide acetylation acylation alkylation Article benzylation carbohydrate synthesis conformation conformational transition deacylation glycosylation ion transport one pot synthesis regioselectivity ring opening stereochemistry The use of thiogalactofuranoside as donors for the construction of internal Galf containing oligosaccharide is limited, probably due to the difficulty to functionalize thiogalactofuranoside derivatives showing O-2, O-3, and O-5 with similar reactivity. An efficient method for complete regioselective 5-O-opening of conformationally restricted 3,5-O-di-tert-butylsilylene-d-galactofuranoside derivatives was developed. The use of a solution nBu4NF (1.1 equiv) in CH2Cl2 on 6 gave the 5-OH free derivative 10 as the only product (90%). 3-O-Di-tert-butylhydroxysilyl derivative 10 was stable upon purification and glycosylation reaction. Preactivation of conformationally restricted thioglycoside 6 employing p-NO2-benzensulfenyl chloride/AgOTf followed by condensation over the 5-OH thioglycoside acceptor 10 gave the corresponding disaccharide 12 without autocondensation byproduct. Regioselective 5-O-deprotection was also successfully performed over the (1→5)-β-d-galactofuranosyl di- and trisaccharide derivatives 12 and 13. This methodology allowed the differentiation between the secondary hydroxyl groups OH-3 and OH-5 of 1,2-cis or 1,2-trans d-galactofuranoside derivatives, and it still constitutes an innovative approach to access oligosaccharides of pharmacological importance. © 2016 American Chemical Society. Fil:Tilve, M.J. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Gallo-Rodriguez, C. 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_00223263_v81_n20_p9585_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 |
Oligosaccharides Autocondensation Glycosylation reactions Hydroxyl groups Innovative approaches Regio-selective Thioglycosides Regioselectivity disaccharide furan derivative galactose oligosaccharide hydroxyl group n acetylgalactosamine oligosaccharide thioglycoside trisaccharide acetylation acylation alkylation Article benzylation carbohydrate synthesis conformation conformational transition deacylation glycosylation ion transport one pot synthesis regioselectivity ring opening stereochemistry |
| spellingShingle |
Oligosaccharides Autocondensation Glycosylation reactions Hydroxyl groups Innovative approaches Regio-selective Thioglycosides Regioselectivity disaccharide furan derivative galactose oligosaccharide hydroxyl group n acetylgalactosamine oligosaccharide thioglycoside trisaccharide acetylation acylation alkylation Article benzylation carbohydrate synthesis conformation conformational transition deacylation glycosylation ion transport one pot synthesis regioselectivity ring opening stereochemistry Tilve, M.J. Cori, C.R. Gallo-Rodriguez, C. Regioselective 5-O-Opening of Conformationally Locked 3,5-O-Di-tert-butylsilylene- d -galactofuranosides. Synthesis of (1→5)-β- d -Galactofuranosyl Derivatives |
| topic_facet |
Oligosaccharides Autocondensation Glycosylation reactions Hydroxyl groups Innovative approaches Regio-selective Thioglycosides Regioselectivity disaccharide furan derivative galactose oligosaccharide hydroxyl group n acetylgalactosamine oligosaccharide thioglycoside trisaccharide acetylation acylation alkylation Article benzylation carbohydrate synthesis conformation conformational transition deacylation glycosylation ion transport one pot synthesis regioselectivity ring opening stereochemistry |
| description |
The use of thiogalactofuranoside as donors for the construction of internal Galf containing oligosaccharide is limited, probably due to the difficulty to functionalize thiogalactofuranoside derivatives showing O-2, O-3, and O-5 with similar reactivity. An efficient method for complete regioselective 5-O-opening of conformationally restricted 3,5-O-di-tert-butylsilylene-d-galactofuranoside derivatives was developed. The use of a solution nBu4NF (1.1 equiv) in CH2Cl2 on 6 gave the 5-OH free derivative 10 as the only product (90%). 3-O-Di-tert-butylhydroxysilyl derivative 10 was stable upon purification and glycosylation reaction. Preactivation of conformationally restricted thioglycoside 6 employing p-NO2-benzensulfenyl chloride/AgOTf followed by condensation over the 5-OH thioglycoside acceptor 10 gave the corresponding disaccharide 12 without autocondensation byproduct. Regioselective 5-O-deprotection was also successfully performed over the (1→5)-β-d-galactofuranosyl di- and trisaccharide derivatives 12 and 13. This methodology allowed the differentiation between the secondary hydroxyl groups OH-3 and OH-5 of 1,2-cis or 1,2-trans d-galactofuranoside derivatives, and it still constitutes an innovative approach to access oligosaccharides of pharmacological importance. © 2016 American Chemical Society. |
| format |
JOUR |
| author |
Tilve, M.J. Cori, C.R. Gallo-Rodriguez, C. |
| author_facet |
Tilve, M.J. Cori, C.R. Gallo-Rodriguez, C. |
| author_sort |
Tilve, M.J. |
| title |
Regioselective 5-O-Opening of Conformationally Locked 3,5-O-Di-tert-butylsilylene- d -galactofuranosides. Synthesis of (1→5)-β- d -Galactofuranosyl Derivatives |
| title_short |
Regioselective 5-O-Opening of Conformationally Locked 3,5-O-Di-tert-butylsilylene- d -galactofuranosides. Synthesis of (1→5)-β- d -Galactofuranosyl Derivatives |
| title_full |
Regioselective 5-O-Opening of Conformationally Locked 3,5-O-Di-tert-butylsilylene- d -galactofuranosides. Synthesis of (1→5)-β- d -Galactofuranosyl Derivatives |
| title_fullStr |
Regioselective 5-O-Opening of Conformationally Locked 3,5-O-Di-tert-butylsilylene- d -galactofuranosides. Synthesis of (1→5)-β- d -Galactofuranosyl Derivatives |
| title_full_unstemmed |
Regioselective 5-O-Opening of Conformationally Locked 3,5-O-Di-tert-butylsilylene- d -galactofuranosides. Synthesis of (1→5)-β- d -Galactofuranosyl Derivatives |
| title_sort |
regioselective 5-o-opening of conformationally locked 3,5-o-di-tert-butylsilylene- d -galactofuranosides. synthesis of (1→5)-β- d -galactofuranosyl derivatives |
| url |
http://hdl.handle.net/20.500.12110/paper_00223263_v81_n20_p9585_Tilve |
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