6-azidohexan-1-ol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Reaction of 6-azidohexanol (0.74 g, 5.22 mmol) and mesyl chloride (0.61 mL, 7.83 mmol) within 3 h as described for synthesis of 156a gave compound 156e (0.87 g) as a crude colorless oil.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Compound [18] (0.25-6.2 g, 0.2-4.91 mmol) and 6-azidohexanol (0.11-2.47 g, 0.4-9.82 mmol) are dissolved in dry acetonitrile and, at 0° C., 3 Å molecular sieves (0.1-2.5 g) and trimethylsilyl trifluoromethanesulfonate (0.01-0.78 g, 0.02-7 mmol) are added. After the reaction is complete, the mixture is filtered and washed with saturated sodium bicarbonate solution. Concentration results in the crude product which is purified by chromatography on silica gel with an ethyl acetate/isohexane gradient (0.18-4.48 g, 0.13-3.19 mmol, about 65% yield). It is subsequently taken up in methanol/hydrazine hydrate (1:1) (1-50 ml) and heated at 80° C. until reaction is complete. After evaporation of the solvent, the crude product is taken up in dichloromethane/methanol (1:1) and stirred at 0° C. with acetic anhydride (1.3-40 mmol) until reaction is complete. Evaporation is followed by reduction of the azide with hydrogen in the presence of catalytic amounts of palladium on carbon (10%) (0.01-1.5 g) in methanol (0.5-35 ml). The crude product compound [19] obtained after evaporation is purified by gel chromatography on Biogel P2 (0.06-1.35 g, 0.09-2.23 mmol, about 70% yield). FAB-MS: M+H+ =608. 1H-NMR [300 MHz, DMSO]: 7.98 (NH3+OAc-), 4.92 (Fuc-H-1), 4.65 (HNAc), 4.36 (GlcNAc-H-1), 4.28 (Gal-H-1), 4.1-3.35 (m), 3.26 (CH2 --NH3+OAc-), 1.79 (GlcNCOCH3) 1.58-1.18 (O--(CH2)5 --CH2 --NH3+OAc-), 0.99 (Fuc-CH3) ppm. the mixture is filtered washed with saturated sodium bicarbonate solution Concentration results in the crude product which

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Compound [13] (0.21-2.66 g, 0.54-7.05 mmol) and 6-azidohexanol (0.27-3.54 g, 1.08-14.1 mmol) are dissolved in dry acetonitrile and, at 0° C., molecular sieves (0.2-5 g) and trimethylsilyl trifluoromethanesulfonate (0.02-1.56 g, 1-70 mmol) are added. After the reaction is complete, the mixture is filtered and washed with saturated sodium bicarbonate solution. Concentration results in the crude product which is purified by chromatography on silica gel with an ethyl acetate/isohexane gradient (0.17-2.23 g, 0.35-4.58 mmol, about 65% yield). The product is subsequently taken up in methanol/hydrazine hydrate (1:1) (1-30 ml) and heated at 80° C. until reaction is complete. After evaporation of the solvent, the crude product is taken up in dichloromethane/methanol (1:1) and stirred at 0° C. with acetic anhydride (3.5-45.8 mmol) until reaction is complete. Evaporation is followed by reduction of the azide with hydrogen in the presence of catalytic amounts of palladium on carbon (10%) (0.01-1.5 g) in methanol (0.5-40 ml). The crude product compound [14] obtained after evaporation is purified by gel chromatography on Biogel P2 (0.12-1.54 g, 0.25-3.2 mmol, about 70% yield). FAB-MS: M+H+ =483. 1H-NMR [300 MHz, D2O]: 4.98 (Fuc-H -1), 4.28 (Gal-H-1), 4.33, 3.99-3.38 (m), 2.99, 2.09 (GlcNCOCH3), 1.72-1.32 (O--(CH2)5 --CH2 --N), 1.11 (Fuc-CH3) ppm. the mixture is filtered washed with saturated sodium bicarbonate solution Concentration results in the crude product which

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The crude product compound [3] (0.27-7.14 g, 0.54-14.2 mmol) and 6-azidohexanol (0.27-3.54 g, 1.08-14.1 mmol) are dissolved in dry acetonitrile, at 0° C., molecular sieves (0.2-5 g, 3 Å) and trimethylsilyl trifluoromethanesulfonate (0.02-1.56 g, 0.1-7 mmol) are added. After the reaction is complete, the mixture is filtered and washed with saturated sodium bicarbonate solution. Concentration results in the crude product, which is purified by chromatography on silica gel with an ethyl acetate/isohexane gradient (0.17-2.23 g, 0.35-4.58 mmol, about 69% yield). The product is then taken up in methanol/hydrazine hydrate (1:1) 1-30 ml) and heated at 80° C. until reaction is complete. After evaporation of the solvent, the crude product is taken up in dichloromethane/methanol (1:1) and stirred at 0° C. with acetic anhydride (3.5-45.8 mmol) until reaction is complete. After evaporation, the azide is reduced with hydrogen in the presence of catalytic amounts of palladium on carbon (10%) (0.01-1.5 g) in methanol (0.5-40 ml). The crude product resulting after evaporation is purified by gel chromatography on Biogel P2 (compound [4];0.08-1.02 g, 0.25-3.2 mmol, about 70% yield). FAB-MS: M+H+ =321. 1H-NMR [300 MHz, DMSO]: 7.68 (HNAc), 4.23 (GlcNAc-H-1), 3.78-3.6 (m), 3.49-3.23 (m), 3.08-3.02 (m) 2.58, 179 (GlcNCOCH3), 1.51-1.21 (O--(CH2)--N). the mixture is filtered washed with saturated sodium bicarbonate solution Concentration results in the crude product, which

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Compound [18] (0.25-6.2 g, 0.2-4.91 mmol) and 6-azidohexanol (0.11-2.47 g, 0.4-9.82 mmol) are dissolved in dry acetonitrile and, at 0° C., 3 Å molecular sieves (0.1-2.5 g) and trimethylsilyl trifluoromethanesulfonate (0.01-0.78 g, 0.02-7 mmol) are added. After the reaction is complete, the mixture is filtered and washed with saturated sodium bicarbonate solution. Concentration results in the crude product which is purified by chromatography on silica gel with an ethyl acetate/isohexane gradient (0.18-4.48 g, 0.13-3.19 mmol, about 65% yield). It is subsequently taken up in methanol/hydrazine hydrate (1:1) (1-50 ml) and heated at 80° C. until reaction is complete. After evaporation of the solvent, the crude product is taken up in dichloromethane/methanol (1:1) and stirred at 0° C. with acetic anhydride (1.3-40 mmol) until reaction is complete. Evaporation is followed by reduction of the azide with hydrogen in the presence of catalytic amounts of palladium on carbon (10%) (0.01-1.5 g) in methanol (0.5-35 ml). The crude product compound [19] obtained after evaporation is purified by gel chromatography on Biogel P2 (0.06-1.35 g, 0.09-2.23 mmol, about 70% yield). FAB-MS: M+H+ =608. 1H-NMR [300 MHz, DMSO]: 7.98 (NH3+OAc-), 4.92 (Fuc-H-1), 4.65 (HNAc), 4.36 (GlcNAc-H-1), 4.28 (Gal-H-1), 4.1-3.35 (m), 3.26 (CH2 --NH3+OAc-), 1.79 (GlcNCOCH3) 1.58-1.18 (O--(CH2)5 --CH2 --NH3+OAc-), 0.99 (Fuc-CH3) ppm. the mixture is filtered washed with saturated sodium bicarbonate solution Concentration results in the crude product which

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Compound [13] (0.21-2.66 g, 0.54-7.05 mmol) and 6-azidohexanol (0.27-3.54 g, 1.08-14.1 mmol) are dissolved in dry acetonitrile and, at 0° C., molecular sieves (0.2-5 g) and trimethylsilyl trifluoromethanesulfonate (0.02-1.56 g, 1-70 mmol) are added. After the reaction is complete, the mixture is filtered and washed with saturated sodium bicarbonate solution. Concentration results in the crude product which is purified by chromatography on silica gel with an ethyl acetate/isohexane gradient (0.17-2.23 g, 0.35-4.58 mmol, about 65% yield). The product is subsequently taken up in methanol/hydrazine hydrate (1:1) (1-30 ml) and heated at 80° C. until reaction is complete. After evaporation of the solvent, the crude product is taken up in dichloromethane/methanol (1:1) and stirred at 0° C. with acetic anhydride (3.5-45.8 mmol) until reaction is complete. Evaporation is followed by reduction of the azide with hydrogen in the presence of catalytic amounts of palladium on carbon (10%) (0.01-1.5 g) in methanol (0.5-40 ml). The crude product compound [14] obtained after evaporation is purified by gel chromatography on Biogel P2 (0.12-1.54 g, 0.25-3.2 mmol, about 70% yield). FAB-MS: M+H+ =483. 1H-NMR [300 MHz, D2O]: 4.98 (Fuc-H -1), 4.28 (Gal-H-1), 4.33, 3.99-3.38 (m), 2.99, 2.09 (GlcNCOCH3), 1.72-1.32 (O--(CH2)5 --CH2 --N), 1.11 (Fuc-CH3) ppm. the mixture is filtered washed with saturated sodium bicarbonate solution Concentration results in the crude product which

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The crude product compound [3] (0.27-7.14 g, 0.54-14.2 mmol) and 6-azidohexanol (0.27-3.54 g, 1.08-14.1 mmol) are dissolved in dry acetonitrile, at 0° C., molecular sieves (0.2-5 g, 3 Å) and trimethylsilyl trifluoromethanesulfonate (0.02-1.56 g, 0.1-7 mmol) are added. After the reaction is complete, the mixture is filtered and washed with saturated sodium bicarbonate solution. Concentration results in the crude product, which is purified by chromatography on silica gel with an ethyl acetate/isohexane gradient (0.17-2.23 g, 0.35-4.58 mmol, about 69% yield). The product is then taken up in methanol/hydrazine hydrate (1:1) 1-30 ml) and heated at 80° C. until reaction is complete. After evaporation of the solvent, the crude product is taken up in dichloromethane/methanol (1:1) and stirred at 0° C. with acetic anhydride (3.5-45.8 mmol) until reaction is complete. After evaporation, the azide is reduced with hydrogen in the presence of catalytic amounts of palladium on carbon (10%) (0.01-1.5 g) in methanol (0.5-40 ml). The crude product resulting after evaporation is purified by gel chromatography on Biogel P2 (compound [4];0.08-1.02 g, 0.25-3.2 mmol, about 70% yield). FAB-MS: M+H+ =321. 1H-NMR [300 MHz, DMSO]: 7.68 (HNAc), 4.23 (GlcNAc-H-1), 3.78-3.6 (m), 3.49-3.23 (m), 3.08-3.02 (m) 2.58, 179 (GlcNCOCH3), 1.51-1.21 (O--(CH2)--N). the mixture is filtered washed with saturated sodium bicarbonate solution Concentration results in the crude product, which

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 6-bromo-1-hexanol (3.6 g, 20 mmol) and sodium azide (2.6 g, 40 mmol) in 95% ethanol (50 mL) was heated with stirring to reflux for 12 hours. The mixture was filtered, and the filtrate concentrated by rotary evaporation. The residue was dissolved in ether (250 mL) and washed three times with water. The ether layer was dried over anhydrous MgSO4, and concentrated by rotary evaporation to give the desired product as a colorless liquid in 88% yield: 1H NMR (CDCl3, 400 MHz): δ (CHCl3 7.26 ppm) 3.65-3.62 (t, J=6.52 Hz, 2H), 3.28-3.24 (t, J=6.88 Hz, 2H), 1.60 (m, 4H), 1.40 (m, 4H); 13C NMR (CDCl3, 100 MHz): δ (ppm) 62.7, 51.3, 32.5, 28.8, 26.5, 25.3. to reflux for 12 hours The mixture was filtered the filtrate concentrated by rotary evaporation The residue was dissolved in ether (250 mL) washed three times with water The ether layer was dried over anhydrous MgSO4 concentrated by rotary evaporation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 500 mL round bottom flask, a solution of 1-azido-6-hydroxyhexane (14.3 g, 100 mmol), methacrylic acid (7.74 g, 90 mmol), and 4-dimethylaminopyridine (DMAP) (3.67 g, 30 mmol) in 100 mL of methylene chloride was cooled to 0° C. Dicyclohexylcarbodiimide (DCC) (20.63 g, 100 mmol) was dissolved in 50 mL methylene chloride and added slowly to the solution. The resulting mixture was warmed to room temperature and stirred overnight. The precipitate was removed by filtration. After removal of the solvent and silica gel column chromatography (10:1 mixture of hexane and ethyl acetate), the product was obtained as a colorless liquid (yield: 16.1 g, 85%). added slowly to the solution The precipitate was removed by filtration After removal of the solvent and silica gel column chromatography (10:1 mixture of hexane and ethyl acetate)

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 6-Bromo-1-hexanol (5.00 g, 27.6 mmol) was dissolved in 12 mL of DMF. To this solution, sodium azide (4.00 g, 61.5 mmol) was added and the mixture was stirred at 50° C. for 3 days. The mixture was concentrated by evaporation, and distilled water (10 mL) was added thereto. This aqueous solution was extracted six times with diethyl ether, and the combined organic extracts were dried over magnesium sulfate, followed by evaporation to give a product (6-azido-1-hexanol). The yield was 99% or more. The mixture was concentrated by evaporation distilled water (10 mL) was added This aqueous solution was extracted six times with diethyl ether the combined organic extracts were dried over magnesium sulfate followed by evaporation