Reaction #162014

Reaction equation

azide

12-Azidododecyl 2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl-(1→3)-2,4,6-tri-O-acetyl-α-D-mannopyranosyl-(1→3)-2,4,6-tri-O-acetyl-α-D-mannopyranosyl-(1→3)-2,4,6-tri-O-acetyl-α-D-mannopyranosyl-(1→2)-3,4,6-tri-O-acetyl-α-D-mannopyranoside

phenylacetylene

sodium ascorbate

→

phenyltriazole

Yield 62.0%

12-(4-Phenyl-[1,2,3]triazol-1-yl)dodecyl 2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl-(1→3)-2,4,6-tri-O-acetyl-α-D-mannopyranosyl-(1→3)-2,4,6-tri-O-acetyl-α-D-mannopyranosyl-(1→3)-2,4,6-tri-O-acetyl-α-D-mannopyranosyl-(1→2)-3,4,6-tri-O-acetyl-α-D-mannopyranoside

Yield 62.0%

Solvents

t-butanol

Conditions

Workup

1. 1
   OtherThe mixture was then evaporated onto silica gel
2. 2
   Otherpurified by flash column chromatography (1×18 cm, gradient elution with hexane-ethyl acetate 6:1, 4:1, 2:1, 1:1, 1:2 to 1:3)

Procedure

In a 1 mL HPLC sample vial was loaded the azide 5 (71 mg, 41.5 μmol), t-butanol (100 μL, 0.4 M), phenylacetylene (83 μmol, 2 eq), copper sulfate solution (0.3 M in water, 14 μL, 4.2 μmol, 10 mol %) and sodium ascorbate solution (1M in water, 12.4 μL, 12.4 μmol, 30 mol %) in that order. The mixture was stirred at room temperature for 2 days. The mixture was then evaporated onto silica gel and purified by flash column chromatography (1×18 cm, gradient elution with hexane-ethyl acetate 6:1, 4:1, 2:1, 1:1, 1:2 to 1:3) to give the phenyltriazole 6 as a colourless gum (46.3 mg, 62%). 1H NMR (CDCl3, 400 MHz) δ 7.82 (d, 2H, J=7.2, Ph), 7.75 (s, 1H, triazole), 7.41 (t, 2H, J=7.2, Ph), 7.31 (t, 1H, J=7.2, Ph), 5.30-5.15 (m, 8H), 5.03-4.87 (m, 8H), 4.38 (t, 2H, J=7.2, NCH2), 4.29-3.77 (m, 19H), 3.64 (dt, 1H, J=9.6, 6.8, OCH2), 3.40 (dt, 1H, J=9.6, 6.8, OCH2), 2.17, 2.16, 2.16, 2.13, 2.11, 2.11, 2.11, 2.10, 2.09, 2.07, 2.05, 2.05, 2.02, 2.00, 1.96 (each s, total 48H, 16×Ac), 1.93 (m, 2H, CH2), 1.57 (m, 2H, CH2), 1.34-1.24 (m, 16H, 8×CH2).

Source