(2S)-3,3-dimethylbutane-1,2-diol

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

Procedure: To a solution of (2S)-3,3-dimethyl-butane-1,2-diol (3.1 g, 26.3 mmol) in dichloromethane (25 ml) is added pyridine (4.3 ml, 52.6 mmol). To the mixture is then added dropwise a solution of 4-toluenesulfonyl chloride (5.0 g, 26.3 mmol) in dichloromethane (25 ml) at 0° C. The reaction mixture is warmed to room temperature and stirred for additional 16 h. The reaction mixture is diluted with dichloromethane (50 ml) and washed with 10% copper(II) sulfate solution (2×30 ml). The organic layer is dried over sodium sulfate and evaporated to get the crude product, which is purified by column chromatography (silica gel, 5% ethyl acetate/hexane) affording 4-methyl-benzenesulfonic acid [(2S)-2-hydroxy-3,3-dimethyl-butyl]ester (4.2 g, 14.4 mmol, 54%). washed with 10% copper(II) sulfate solution (2×30 ml) The organic layer is dried over sodium sulfate evaporated to get the crude product, which is purified by column chromatography (silica gel, 5% ethyl acetate/hexane)

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

Procedure: To a solution of (2S)-3,3-dimethyl-butane-1,2-diol (3.1 g, 26.3 mmol) in dichloromethane (25 ml) is added pyridine (4.3 ml, 52.6 mmol). To the mixture is then added dropwise a solution of 4-toluenesulfonyl chloride (5.0 g, 26.3 mmol) in dichloromethane (25 ml) at 0° C. The reaction mixture is warmed to room temperature and stirred for additional 16 h. The reaction mixture is diluted with dichloromethane (50 ml) and washed with 10% copper(II) sulfate solution (2×30 ml). The organic layer is dried over sodium sulfate and evaporated to get the crude product, which is purified by column chromatography (silica gel, 5% ethyl acetate/hexane) affording 4-methyl-benzenesulfonic acid [(2S)-2-hydroxy-3,3-dimethyl-butyl]ester (4.2 g, 14.4 mmol, 54%). washed with 10% copper(II) sulfate solution (2×30 ml) The organic layer is dried over sodium sulfate evaporated to get the crude product, which is purified by column chromatography (silica gel, 5% ethyl acetate/hexane)

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

Procedure: To 5.63 g (47.63 mmol) of (2S)-3,3-dimethyl-1,2-butanediol in 48 mL of carbon tetrachloride was added 3.47 mL (47.63 mmol) of thionyl chloride. The resulting mixture was heated at reflux for 1 h, and cooled to 0° C., before 48 mL of acetonitrile was added. Then, 1.0 mg (4.8 μmol) of ruthenium(III) chloride hydrate was added, followed by 15.28 g (71.45 mmol) of sodium periodate. The reaction mixture was diluted with 71 mL of water and stirred for 2 h. It was then extracted with diethyl ether. The extract was washed with saturated aqueous sodium bicarbonate, dried over anhydrous magnesium sulfate, filtered, and concentrated. The residue was purified by silica gel column chromatography eluting with an ethyl acetate:hexanes solution (3:7) to give 8.33 g (97%) of (4S)-4-tert-butyl-1,3,2-dioxathiolane 2,2-dioxide. Rf=0.30 (3:7 ethyl acetate:hexanes); 1H-NMR (300 MHz, DMSO-d6): δ 4.99–4.88 (m, 2H), 4.78 (t, J=8 Hz, 1H), 0.94 (s, 9H). The resulting mixture was heated at reflux for 1 h was added It was then extracted with diethyl ether The extract was washed with saturated aqueous sodium bicarbonate dried over anhydrous magnesium sulfate filtered concentrated The residue was purified by silica gel column chromatography eluting with an ethyl acetate

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

Procedure: To 6.65 g (56 mmol) of (2S)-3,3-dimethyl-1,2-butanediol in 13 mL of pyridine at 0° C. was added dropwise a solution of 10.68 g (56 mmol) of p-toluenesulfonyl chloride in 20 mL of pyridine. The solution was maintained at 0° C. for 5 h and then let warm to ambient temperature. After being stirred overnight, the mixture was concentrated, and the residue was taken up in 200 mL of diethyl ether. The ether solution was washed with 50 mL of 1N hydrochloric acid, 50 mL of saturated aqueous sodium bicarbonate, and 50 mL of water, dried over anhydrous magnesium sulfate, and concentrated. The residue was purified by silica gel chromatography eluting with ethyl acetate:hexanes (3.5:6.5) to give 13 g (85%) of (2S)-2-hydroxy-3,3-dimethylbutyl 4-methylbenzenesulfonate. 1H-NMR (300 MHz, DMSO-d6): δ 7.79 (d, J=8 Hz, 2H), 7.47 (d, J=8 Hz, 2H), 5.11 (br s, 1H), 4.08 (dd, J=10 Hz, J=3 Hz, 1H), 3.76 (dd, J=10 Hz, J=8 Hz, 1H), 3.23 (d, J=8 Hz, 1H), 2.41 (s, 3H), 0.76 (s, 9H). ES-LCMS m/z 273 (M+H), 295 (M+Na). let warm to ambient temperature the mixture was concentrated The ether solution was washed with 50 mL of 1N hydrochloric acid, 50 mL of saturated aqueous sodium bicarbonate, and 50 mL of water dried over anhydrous magnesium sulfate concentrated The residue was purified by silica gel chromatography eluting with ethyl acetate:hexanes (3.5:6.5)

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

Procedure: To a solution of (2S)-3,3-dimethyl-butane-1,2-diol (3.1 g, 26.3 mmol) in dichloromethane (25 ml) is added pyridine (4.3 ml, 52.6 mmol). To the mixture is then added dropwise a solution of 4-toluenesulfonyl chloride (5.0 g, 26.3 mmol) in dichloromethane (25 ml) at 0° C. The reaction mixture is warmed to room temperature and stirred for additional 16 h. The reaction mixture is diluted with dichloromethane (50 ml) and washed with 10% copper(II) sulfate solution (2×30 ml). The organic layer is dried over sodium sulfate and evaporated to get the crude product, which is purified by column chromatography (silica gel, 5% ethyl acetate/hexane) affording 4-methyl-benzenesulfonic acid [(2S)-2-hydroxy-3,3-dimethyl-butyl]ester (4.2 g, 14.4 mmol, 54%). washed with 10% copper(II) sulfate solution (2×30 ml) The organic layer is dried over sodium sulfate evaporated to get the crude product, which is purified by column chromatography (silica gel, 5% ethyl acetate/hexane)