4-[tert-butyl(dimethyl)silyl]oxybut-2-yn-1-ol

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

Conditions: temp:22.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 175 g of tert-butyldimethylsilyl chloride in 100 ml of a 1:1 mixture that consists of hexane and dimethylformamide is slowly added in drops at 0° C. under nitrogen to a solution of 100 g of 2-butin-1-ol and 158 g of imidazole in 300 ml of dimethylformamide, and it is stirred for 2 hours at 0° C. and for 16 hours at 22° C. The reaction mixture is diluted with 2.5 l of ether, washed once with water, once with 5% sulfuric acid, once with water, once with saturated sodium bicarbonate solution and washed neutral with semi-saturated sodium chloride solution. After drying on sodium sulfate and filtration, it is concentrated by evaporation in a vacuum. The residue that is thus obtained is purified by chromatography on silica gel. With hexane/0–40% ether, 74.3 g of the title compound is obtained as a colorless oil. washed once with water, once with 5% sulfuric acid, once with water, once with saturated sodium bicarbonate solution washed neutral with semi-saturated sodium chloride solution After drying on sodium sulfate and filtration, it is concentrated by evaporation in a vacuum The residue that is thus obtained is purified by chromatography on silica gel

Conditions: temp:22.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 175 g of tert-butyldimethylsilyl chloride in 100 ml of a 1:1 mixture that consists of hexane and dimethylformamide is slowly added in drops at 0° C. under nitrogen to a solution of 100 g of 2-butin-1-ol and 158 g of imidazole in 300 ml of dimethylformamide, and it is stirred for 2 hours at 0° C. and for 16 hours at 22° C. The reaction mixture is diluted with 2.5 l of ether, washed once with water, once with 5% sulfuric acid, once with water, once with saturated sodium bicarbonate solution and washed neutral with semi-saturated sodium chloride solution. After drying on sodium sulfate and filtration, it is concentrated by evaporation in a vacuum. The residue that is thus obtained is purified by chromatography on silica gel. With hexane/0–40% ether, 74.3 g of the title compound is obtained as a colorless oil. washed once with water, once with 5% sulfuric acid, once with water, once with saturated sodium bicarbonate solution washed neutral with semi-saturated sodium chloride solution After drying on sodium sulfate and filtration, it is concentrated by evaporation in a vacuum The residue that is thus obtained is purified by chromatography on silica gel

Conditions: temp:22.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 175 g of tert-butyldimethylsilyl chloride in 100 ml of a 1:1 mixture of hexane and dimethylformamide is slowly added in drops to a solution of 100 g of 2-butin-1-ol and 158 g of imidazole in 300 ml of dimethylformamide at 0° C. under nitrogen, and it is stirred for 2 hours at 0° C. and for 16 hours at 22° C. The reaction mixture is diluted with 2.5 l of ether, washed once with water, once with 5% sulfuric acid, once with water, once with saturated sodium bicarbonate solution and washed neutral with semi-saturated sodium chloride solution. After drying on sodium sulfate and filtration, it is concentrated by evaporation in a vacuum. The residue that is thus obtained is purified by chromatography on silica gel. 74.3 g of the title compound is obtained with hexane/0-40% ether as a colorless oil. washed once with water, once with 5% sulfuric acid, once with water, once with saturated sodium bicarbonate solution washed neutral with semi-saturated sodium chloride solution After drying on sodium sulfate and filtration, it is concentrated by evaporation in a vacuum The residue that is thus obtained is purified by chromatography on silica gel

Conditions: temp:22.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 175 g of tert-butyldimethylsilyl chloride in 100 ml of a 1:1 mixture of hexane and dimethylformamide is slowly added in drops to a solution of 100 g of 2-butin-1-ol and 158 g of imidazole in 300 ml of dimethylformamide at 0° C. under nitrogen, and it is stirred for 2 hours at 0° C. and for 16 hours at 22° C. The reaction mixture is diluted with 2.5 l of ether, washed once with water, once with 5% sulfuric acid, once with water, once with saturated sodium bicarbonate solution and washed neutral with semi-saturated sodium chloride solution. After drying on sodium sulfate and filtration, it is concentrated by evaporation in a vacuum. The residue that is thus obtained is purified by chromatography on silica gel. 74.3 g of the title compound is obtained with hexane/0-40% ether as a colorless oil. washed once with water, once with 5% sulfuric acid, once with water, once with saturated sodium bicarbonate solution washed neutral with semi-saturated sodium chloride solution After drying on sodium sulfate and filtration, it is concentrated by evaporation in a vacuum The residue that is thus obtained is purified by chromatography on silica gel

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-{[Tert-butyl(dimethyl)silyl]oxy}but-2-yn-1-ol (701.4 mg) was dissolved in ethyl acetate (15 mL), and the solution was cooled to 0° C. Triethylamine (1.1 mL) and methanesulfonyl chloride (0.3 mL) were added, and the mixture was stirred at 0° C. for 3 hrs. Water was added to the reaction mixture and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was separated and purified by silica gel column chromatography (eluent, hexane:ethyl acetate=90:10→50:50) to give the title compound (469.7 mg) as a colorless oil. the mixture was extracted with diethyl ether The organic layer was washed with saturated brine dried over anhydrous magnesium sulfate concentrated under reduced pressure The residue was separated purified by silica gel column chromatography (eluent, hexane:ethyl acetate=90:10→50:50)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 60% Sodium hydride (1.39 g) was suspended in tetrahydrofuran (50 mL), and the suspension was cooled to 0° C., a solution of but-2-yne-1,4-diol (3.0 g) in tetrahydrofuran (20 mL) was added dropwise, and the mixture was stirred at room temperature for 1 hr. tert-Butyldimethylsilyl chloride (5.26 g) was added to the reaction mixture, and the mixture was stirred at room temperature for 24 hrs. Water was added to the reaction mixture and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was separated and purified by silica gel column chromatography (eluent, hexane:ethyl acetate=100:0→80:20) to give the title compound (1.48 g) as a colorless oil. the mixture was stirred at room temperature for 24 hrs the mixture was extracted with diethyl ether The organic layer was washed with saturated brine dried over anhydrous magnesium sulfate concentrated under reduced pressure The residue was separated purified by silica gel column chromatography (eluent, hexane:ethyl acetate=100:0→80:20)

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

Procedure: To an ice cold, stirred solution of the known 4-(tert-Butyl-dimethyl-silanyloxy)-but-2-yn-1-ol (3.14 g, 15.7 mmol) in THF (50 ml) was added DBU (2.6 ml, 17.4 mmol) and DPPA (3.8 ml, 17.6 mmol). The solution was warmed to room temperature and stirred under an inert atmosphere overnight. The reaction was poured into sat. NaHCO3 and the layers separated. The aqueous layer was re-extracted with EtOAc (2×) and the combined organic layers were dried (Na2SO4), and concentrated under vacuum. Triphenylphosphine (4.61 g, 17.6 mmol) was added to this crude azide dissolved in THF (50 ml), followed by addition of H20 (0.44 ml). The resultant solution was stirred overnight at room temperature, concentrated under reduced pressure and the residue was slurried in a 1:1 mixture of Et2O/pet ether. The solids were removed and the filtrate was concentrated and purified by flash chromatography on silica gel eluting CH2Cl2/MeOH (19:1) to give an amber oil. 1H NMR (CDCl3) δ 4.19 (2H, t, J=1.9 Hz), 3.33 (2H, t, J=1.9 Hz), 0.79 (9H, s), 0.00 (6H, s). the layers separated The aqueous layer was re-extracted with EtOAc (2×) the combined organic layers were dried (Na2SO4) concentrated under vacuum followed by addition of H20 (0.44 ml) concentrated under reduced pressure the residue was slurried in a 1:1 mixture of Et2O/pet ether The solids were removed the filtrate was concentrated purified by flash chromatography on silica gel eluting CH2Cl2/MeOH (19:1) to give an amber oil

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-{[Tert-butyl(dimethyl)silyl]oxy}but-2-yn-1-ol (701.4 mg) was dissolved in ethyl acetate (15 mL), and the solution was cooled to 0° C. Triethylamine (1.1 mL) and methanesulfonyl chloride (0.3 mL) were added, and the mixture was stirred at 0° C. for 3 hrs. Water was added to the reaction mixture and the mixture was extracted with diethyl ether. The organic layer washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was separated and purified by silica gel column chromatography (eluent, hexane:ethyl acetate=90:10→50:50) to give the title compound (469.7 mg) as a colorless oil. the mixture was extracted with diethyl ether The organic layer washed with saturated brine dried over anhydrous magnesium sulfate concentrated under reduced pressure The residue was separated purified by silica gel column chromatography (eluent, hexane:ethyl acetate=90:10→50:50)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 60% Sodium hydride (1.39 g) was suspended in tetrahydrofuran (50 mL), and the suspension was cooled to 0° C., a solution of but-2-yne-1,4-diol (3.0 g) in tetrahydrofuran (20 mL) was added dropwise, and the mixture was stirred at room temperature for 1 hr. tert-Butyldimethylsilyl chloride (5.26 g) was added to the reaction mixture, and the mixture was stirred at room temperature for 24 hrs. Water was added to the reaction mixture and the mixture was extracted with diethyl ether. The organic layer washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was separated and purified by silica gel column chromatography (eluent, hexane:ethyl acetate=100:0→80:20) to give the title compound (1.48 g) as a colorless oil. the mixture was stirred at room temperature for 24 hrs the mixture was extracted with diethyl ether The organic layer washed with saturated brine dried over anhydrous magnesium sulfate concentrated under reduced pressure The residue was separated purified by silica gel column chromatography (eluent, hexane:ethyl acetate=100:0→80:20)

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

Procedure: 1-(tert-Butyldimethylsilyloxy)-but-2-yn-4-ol (63, 4.0 g, 19.96 mmol), imidazole (1.80 g, 26.45 mmol), iodine (6.58 g, 25.95 mmol) and triphenylphosphine (6.80 g, 25.95 mmol) are treated in 100 ml dichloromethane according to J. Robertson et al. J. Chem. Soc., Perkin Trans. 1, 3389-3369, 2000. Work-up yields 4.42 g (71%) of a colourless oil. The product is used directly in the next step.

Conditions: temp:22.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 175 g of tert-butyldimethylsilyl chloride in 100 ml of a 1:1 mixture that consists of hexane and dimethylformamide is slowly added in drops at 0° C. under nitrogen to a solution of 100 g of 2-butin-1-ol and 158 g of imidazole in 300 ml of dimethylformamide, and it is stirred for 2 hours at 0° C. and for 16 hours at 22° C. The reaction mixture is diluted with 2.5 l of ether, washed once with water, once with 5% sulfuric acid, once with water, once with saturated sodium bicarbonate solution and washed neutral with semi-saturated sodium chloride solution. After drying on sodium sulfate and filtration, it is concentrated by evaporation in a vacuum. The residue that is thus obtained is purified by chromatography on silica gel. With hexane/0–40% ether, 74.3 g of the title compound is obtained as a colorless oil. washed once with water, once with 5% sulfuric acid, once with water, once with saturated sodium bicarbonate solution washed neutral with semi-saturated sodium chloride solution After drying on sodium sulfate and filtration, it is concentrated by evaporation in a vacuum The residue that is thus obtained is purified by chromatography on silica gel