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Volumn 46, Issue 13, 2005, Pages 2331-2336

One-pot synthesis of triazole-linked glycoconjugates

Author keywords

1,2,3 Triazole; 1,3 Dipolar cycloaddition; Bioconjugation; Carbohydrate; Click chemistry; Glycosylation; Neoglycoconjugate

Indexed keywords

1,2,3 TRIAZOLE DERIVATIVE; CARBOHYDRATE; COPPER COMPLEX; GLYCOCONJUGATE;

EID: 14744289657     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2005.01.175     Document Type: Article
Times cited : (178)

References (68)
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    • Carbohydrate Antigens
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    • M. Meldal, S. Mouritsen, and K. Bock P.J. Garegg A.A. Lindberg Carbohydrate Antigens ACS Symposium Series 519 1993 American Chemical Society Washington, DC 19
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    • Meldal, M.1    Mouritsen, S.2    Bock, K.3
  • 20
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    • Kanie, O.1
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    • For enzymatic approaches to glycosylation see reviews: V. Kren, and J. Thiem Chem. Soc. Rev. 26 1997 463
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    • Kren, V.1    Thiem, J.2
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    • Typical experimental procedure from unprotected saccharides: the glucose (1 g, 5.6 mmol) and iodine (50 mg) were suspended in acetic anhydride (5 mL) and stirred at room temperature until TLC showed the reaction to be completed. The reaction mixture was stirred for another 1 h at room temperature after the addition of dry dichloromethane (DCM, 15 mL) and HBr (33% solution in acetic acid, 7.5 mL). The volatiles were removed by rotary evaporation, the following reagents were added in order of: chloroform (10 mL), saturated sodium bicarbonate solution (23 mL), sodium azide (0.54 g, 8.3 mmol), tetrabutylammonium hydrogen sulfate (1.8 g, 5.5 mmol), phenyl acetylene (0.56 g, 5.6 mmol), copper sulfate pentahydrate (40 mg, 0.16 mmol), sodium ascorbate (0.11 g, 0.54 mmol), and ethanol (5 mL). Upon being stirred at room temperature for about 16 h, a white precipitate was collected by filtration and washed with 0.1 M ammonium hydroxide solution (10 mL) to afford pure product 1 ; 91% yield. (WARNINGS: The use of dichloromethane or bromoform as solvent in the presence of azide anions is absolutely prohibited due to the probability of generating explosive diazidomethane or triazidomethane at ambient temperature; see: A. Hassner, M. Stern, and H.E. Gottlieb J. Org. Chem. 55 1990 2304)
    • (1990) J. Org. Chem. , vol.55 , pp. 2304
    • Hassner, A.1    Stern, M.2    Gottlieb, H.E.3
  • 52
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    • note
    • Typical experimental procedure from saccharides acetates: A solution of d-ribose pentaacetate (0.49 g, 1.5 mmol) and HBr (33% solution in acetic acid, 1.5 mL) in dry chloroform (10 mL) was stirred under nitrogen for about 4 h at room temperature until the completion of the reaction monitored by TLC. After the volatiles were removed, the following reagents were added in order of: chloroform (10 mL), saturated sodium bicarbonate solution (5 mL), sodium azide (0.14 g, 2.2 mmol), tetrabutylammonium hydrogen sulfate (0.5 g, 1.5 mmol), phenyl acetylene (0.15 g, 1.5 mmol), copper sulfate pentahydrate (12 mg, 0.05 mmol), sodium ascorbate (30 mg, 0.15 mmol), and ethanol (5 mL). The reaction mixture was stirred at room temperature for about 16 h. Solvents were removed and the residue was cooled in ice water bath. The precipitate was collected by filtration and washed with 0.1 M ammonium hydroxide (10 mL) to afford the product 10 in 81% yield. The aqueous layer could be further extracted with chloroform to recover more products


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