2,3-bis(sulfanyl)propan-1-ol

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

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

Procedure: To a solution of 2,3-dimercapto-1-propanol (15.0 ml, 150 mmol) and imidazole (15.3 g, 224 mmol, 1.5 eq) in THF (300 mL) was added t-butyldimethylsilyl chloride (21.4 g, 142 mmol, 0.95 eq) at 0° C. The mixture was stirred at 0° C. for 1 hr and at room temperature for 18 hr. A saturated solution of ammonium chloride was added and the aqueous phase was extracted with dichloromethane. The organic layer was dried with anhydrous sodium sulphate and the solvent was evaporated under reduced pressure. The crude material was purified by flash chromatography with a mixture of hexane and ethyl acetate (90:10) to give the pure compound (32.04 g) in 94.5% yield. the aqueous phase was extracted with dichloromethane The organic layer was dried with anhydrous sodium sulphate the solvent was evaporated under reduced pressure The crude material was purified by flash chromatography with a mixture of hexane and ethyl acetate (90:10)

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

Procedure: To a mixture of 10.18 g (0.082 mole) of 2,3-dimercapto-1-propanol, 20 mL of cyclohexane, and 5.0 g (0.086 mole) of acetone was added 4 drops of concentrated hydrochloric acid, and the mixture was stirred at reflux temperature for 3.5 hours to give, after fractional distillation of the reaction mixture, 5.85 g of a colorless oil, bp 96°-106° C./1.2-1.5 mm Hg, which solidified on standing. Recrystallization from toluene-hexane gave 3.96 g of product, mp 45°-50° C. at reflux temperature for 3.5 hours to give after fractional distillation of the reaction mixture, 5.85 g of a colorless oil, bp 96°-106° C./1.2-1.5 mm Hg, which Recrystallization from toluene-hexane

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

Procedure: To a mixture of 10.18 g (0.082 mole) of 2,3-dimercapto-1-propanol, 20 mL of cyclohexane, and 5.0 g (0.086 mole) of acetone was added 4 drops of concentrated hydrochloric acid, and the mixture was stirred at reflux temperature for 3.5 hours to give, after fractional distillation of the reaction mixture, 5.85 g of a colorless oil, bp 96°-106° C./1.2-1.5 mm Hg, which solidified on standing. Recrystallization from toluene-hexane gave 3.96 g of product, mp 45°-50° C. at reflux temperature for 3.5 hours to give after fractional distillation of the reaction mixture, 5.85 g of a colorless oil, bp 96°-106° C./1.2-1.5 mm Hg, which Recrystallization from toluene-hexane

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

Procedure: A reaction mixture (100 mL, 100 mM Tris, pH 7.5, 10 mM MgCl2, 10 mM MnCl2, 5 mM EDTA, 5 ThM NaN3, 1 mm ATPe 0.01 mM theophylline and 0.03 mM 2, 3-dimercaptopropanol) containing α-methyl-D-mannopyranoside (0.4 g, 20 M), Man-1-P (about 1.5 g, about 50 mM), PEP (1.0 g, 42.7 HM), GDP (30 mg, 1 mM), dried yeast cells (0.4 g), pyruvate kinase PK (300 U), recombinant α1,2-ManT (1.2 U) and inorganic pyrophosphatase (2 U) was slightly stirred at room temperature for 72 hours, then centrifuged. The supernatant was lyophilized and extracted with methanol. After removal of the methanol, the product was purified by silica gel column chromatography (CHCl :CH3OH:H2O=6: 3:0.5, v/v/v) to afford Manα1, 2ManαOMe (Compound 3) (96 mg) in 38 percent overall yield based on consumed α-methyl-D-mannopyranoside. 1H NMR (D2O) δ3.41 (s, 3H), 3.60-3.80 (m, 6H), 3.86 (dd, 1H, J=3.5, 10 Hz), 3.88 (dd, 1H, J=3.5, 10 Hz), 3.90 (d, 1H, d, J=1.5 Hz), 3.92 (d, 1H, J=l Hz), 3.97 (dd, 1H, J=2, 3.5 Hz), 4.08 (dd, 2H, J=2, 3.5 Hz), 5.02 (d, 1H, d, J=2 Hz), 5 .04 (d, 1H, J=2.0 Hz). 13C {1H} NMR (D2O) δ54.90, 61.01, 61.24, 66.98, 67.03, 70.02, 70.29, 70.37, 72.63, 73.40, 78.62, 99.40, 102.43. HRMS calculated for C13H24O11Na+ (M+Na+) 379.1216, found 379.1220. dried yeast cells (0.4 g), pyruvate kinase PK (300 U), recombinant α1,2-ManT (1.2 U) and inorganic pyrophosphatase (2 U) extracted with methanol After removal of the methanol the product was purified by silica gel column chromatography (CHCl

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

Procedure: To a solution of 2,3-dimercapto-1-propanol (15.0 ml, 150 mmol) and imidazole (15.3 g, 224 mmol, 1.5 eq) in THF (300 mL) was added t-butyldimethylsilyl chloride (21.4 g, 142 mmol, 0.95 eq) at 0° C. The mixture was stirred at 0° C. for 1 hr and at room temperature for 18 hr. A saturated solution of ammonium chloride was added and the aqueous phase was extracted with dichloromethane. The organic layer was dried with anhydrous sodium sulphate and the solvent was evaporated under reduced pressure. The crude material was purified by flash chromatography with a mixture of hexane and ethyl acetate (90:10) to give the pure compound (32.04 g) in 94.5w yield. the aqueous phase was extracted with dichloromethane The organic layer was dried with anhydrous sodium sulphate the solvent was evaporated under reduced pressure The crude material was purified by flash chromatography with a mixture of hexane and ethyl acetate (90:10)

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

Procedure: To a solution of 2,3-dimercapto-1-propanol (15.0 ml, 150 mmol) and imidazole (15.3 g, 224 mmol, 1.5 eq) in THF (300 mL) was added t-butyldimethylsilyl chloride (21.4 g, 142 mmol, 0.95 eq) at 0° C. The mixture was stirred at 0° C. for 1 hr and at room temperature for 18 hr. A saturated solution of ammonium chloride was added and the aqueous phase was extracted with dichloromethane. The organic layer was dried with anhydrous sodium sulphate and the solvent was evaporated under reduced pressure. The crude material was purified by flash chromatography with a mixture of hexane and ethyl acetate (90:10) to give the pure compound (32.04 g) in 94.5% yield. the aqueous phase was extracted with dichloromethane The organic layer was dried with anhydrous sodium sulphate the solvent was evaporated under reduced pressure The crude material was purified by flash chromatography with a mixture of hexane and ethyl acetate (90:10)

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

Procedure: To a solution of 2,3-dimercapto-1-propanol (15.0 ml, 150 mmol) and imidazole (15.3 g, 224 mmol, 1.5 eq) in THF (300 mL) was added t-butyldimethylsilyl chloride (21.4 g, 142 mmol, 0.95 eq) at 0° C. The mixture was stirred at 0° C. for 1 hr and at room temperature for 18 hr. A saturated solution of ammonium chloride was added and the aqueous phase was extracted with dichloromethane. The organic layer was dried with anhydrous sodium sulphate and the solvent was evaporated under reduced pressure. The crude material was purified by flash chromatography with a mixture of hexane and ethyl acetate (90:10) to give the pure compound (32.04 g) in 94.5% yield. 1H NMR (300 MHz, CDCl3) δ: 0.08 (s, 6H, CH3), 0.91 (s, 9H, t-butyl), 1.58 (t, 1H, J=8.5 Hz, SH), 1.82 (d, 1H, J=9.2 Hz, SH), 2.85 (m, 2H, H-3), 2.96 (m, 1H, H-2), 3.63 (dd, 1H, J=6.7 Hz, 10.1 Hz, H-1a), 3.86 (dd, 1H, J=4.4 Hz, 10.2 Hz, H-1b). the aqueous phase was extracted with dichloromethane The organic layer was dried with anhydrous sodium sulphate the solvent was evaporated under reduced pressure The crude material was purified by flash chromatography with a mixture of hexane and ethyl acetate (90:10)

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

Procedure: To a solution of 2,3-dimercapto-1-propanol (15.0 ml, 150 mmol) and imidazole (15.3 g, 224 mmol, 1.5 eq) in THF (300 mL) was added t-butyldimethylsilyl chloride (21.4 g, 142 mmol, 0.95 eq) at 0° C. The mixture was stirred at 0° C. for 1 hr and at room temperature for 18 hr. A saturated solution of ammonium chloride was added and the aqueous phase was extracted with dichloromethane. The organic layer was dried with anhydrous sodium sulphate and the solvent was evaporated under reduced pressure. The crude material was purified by flash chromatography with a mixture of hexane and ethyl acetate (90:10) to give the pure compound (32.04 g) in 94.5% yield. 1H NMR (300 MHz, CDCl3) δ: 0.08 (s, 6H, CH3), 0.91 (s, 9H, t-butyl), 1.58 (t, 1H, J=8.5 Hz, SH), 1.82 (d, 1H, J=9.2 Hz, SH), 2.85 (m, 2H, H-3), 2.96 (m, 1H, H-2), 3.63 (dd, 1H, J=6.7 Hz, 10.1 Hz, H-1a), 3.86 (dd, 1H, J=4.4 Hz, 10.2 Hz, H-1b). the aqueous phase was extracted with dichloromethane The organic layer was dried with anhydrous sodium sulphate the solvent was evaporated under reduced pressure The crude material was purified by flash chromatography with a mixture of hexane and ethyl acetate (90:10)

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

Procedure: To a solution of 2,3-dimercapto-1-propanol (15.0 ml, 150 mmol) and imidazole (15.3 g, 224 mmol, 1.5 eq) in THF (300 mL) was added t-butyldimethylsilyl chloride (21.4 g, 142 mmol, 0.95 eq) at 0° C. The mixture was stirred at 0° C. for 1 hr and at room temperature for 18 hr. A saturated solution of ammonium chloride was added and the aqueous phase was extracted with dichloromethane. The organic layer was dried with anhydrous sodium sulphate and the solvent was evaporated under reduced pressure. The crude material was purified by flash chromatography with a mixture of hexane and ethyl acetate (90:10) to give the pure compound (32.04 g) in 94.5% yield. the aqueous phase was extracted with dichloromethane The organic layer was dried with anhydrous sodium sulphate the solvent was evaporated under reduced pressure The crude material was purified by flash chromatography with a mixture of hexane and ethyl acetate (90:10)

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

Procedure: To a solution of 2,3-dimercapto-1-propanol (15.0 ml, 150 mmol) and imidazole (15.3 g, 224 mmol, 1.5 eq) in THF (300 mL) was added t-butyldimethylsilyl chloride (21.4 g, 142 mmol, 0.95 eq) at 0° C. The mixture was stirred at 0° C. for 1 hr and at room temperature for 18 hr. A saturated solution of ammonium chloride was added and the aqueous phase was extracted with dichloromethane. The organic layer was dried with anhydrous sodium sulphate and the solvent was evaporated under reduced pressure. The crude material was purified by flash chromatography with a mixture of hexane and ethyl acetate (90:10) to give the pure compound (32.04 g) in 94.5% yield. the aqueous phase was extracted with dichloromethane The organic layer was dried with anhydrous sodium sulphate the solvent was evaporated under reduced pressure The crude material was purified by flash chromatography with a mixture of hexane and ethyl acetate (90:10)

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

Procedure: To a mixture of 10.18 g (0.082 mole) of 2,3-dimercapto-1-propanol, 20 mL of cyclohexane, and 5.0 g (0.086 mole) of acetone was added 4 drops of concentrated hydrochloric acid, and the mixture was stirred at reflux temperature for 3.5 hours to give, after fractional distillation of the reaction mixture, 5.85 g of a colorless oil, bp 96°-106° C./1.2-1.5 mm Hg, which solidified on standing. Recrystallization from toluene-hexane gave 3.96 g of product, mp 45°-50° C. at reflux temperature for 3.5 hours to give after fractional distillation of the reaction mixture, 5.85 g of a colorless oil, bp 96°-106° C./1.2-1.5 mm Hg, which Recrystallization from toluene-hexane