tert-butyl N-(oxiran-2-ylmethyl)carbamate

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

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

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

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

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

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

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of Oxiranylmethyl-carbamic acid tert-butyl ester (0.64 g, 3.7 mmol) in Ethanol (6 mL) was treated at room temperature with a 2.0M solution of methylamine in THF (5 mL, 10 mmol). The reaction mixture was stirred for 5 hours at 40° C. The solvent was evaporated in vacuo to yield a gum which was used directly into the next step (0.75 g, 98%) The solvent was evaporated in vacuo to yield a gum which

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: First, 21 g (121 mmol) of tert-butyl 2-oxiranylmethylcarbamate was dissolved in 90 mL of dimethylformamide and 11.8 g (182 mmol) of sodium azide was added. The reaction mixture was stirred at 65° C. overnight. The dimethylformamide was removed and ether was added. The ether layer was washed with brine (3×), dried over anhydrous magnesium sulfate, and concentrated. The residue was dissolved in 50 mL of methanol and hydrogenated with 2 g of 10% palladium on carbon under 45 psi of hydrogen gas at room temperature overnight. The catalyst was removed by filtration and the filtrate was concentrated. The residue was dissolved in 30 mL of dichloromethane, and 17.7 mL (17.7 mmol) of 1M 2-pyridinylsulfonyl chloride in dichloromethane and 3.8 mL (21.8 mmol) of N,N-diisopropylethylamine were added. The reaction mixture was stirred at room temperature overnight. After removal of solvent, purification by column chromatography with hexane:ethyl acetate (1:2) as eluant gave 350 mg (0.9%) of tert-butyl 2-hydroxy-3-[(2-pyridinylsulfonyl)amino]propylcarbamate. 1H-NMR (300 MHz CDCl3): δ 8.72 (d, J=6 Hz, 1H), 8.05 (d, J=8 Hz, 1H), 7.97 (t, J=8 Hz, 1H), 7.55 (m, 1H), 6.10 (br s, 1H), 5.11 (br s, 1H), 4.33 (d, J=5 Hz, 1H), 3.81 (m, 1H), 3.36–3.20 (m, 4H), 1.44 (s, 9H). ES-LCMS: 332 (M+H). The dimethylformamide was removed ether was added The ether layer was washed with brine (3×) dried over anhydrous magnesium sulfate concentrated The residue was dissolved in 50 mL of methanol and hydrogenated with 2 g of 10% palladium on carbon under 45 psi of hydrogen gas at room temperature overnight The catalyst was removed by filtration the filtrate was concentrated The residue was dissolved in 30 mL of dichloromethane The reaction mixture was stirred at room temperature overnight After removal of solvent, purification by column chromatography with hexane:ethyl acetate (1:2) as eluant

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

Procedure: To a solution of 28.9 g (184 mmol) of tert-butyl allylcarbamate in 400 mL of dichloromethane was added 103 g (460 mmol) of 77% 3-chloroperoxybenzoic acid at room temperature. The reaction mixture was stirred at room temperature overnight. The solid was filtered and the filtrate was concentrated. The residue was taken up in diethyl ether and washed with 5% sodium hydrosulfite (3×), saturated sodium bicarbonate (3×), brine (3×), and dried over anhydrous magnesium sulfate. Removal of solvent gave 21 g (66%) of tert-butyl 2-oxiranylmethylcarbamate as a liquid. 1H-NMR (400 MHz, CDCl3): δ 4.73 (br s, 1H), 3.53 (br s, 1H), 3.21 (m, 1H), 3.08 (br s, 1H), 2.77 (t, J=4 Hz, 1H), 2.58 (m, 1H), 1.43 (s, 9H). The solid was filtered the filtrate was concentrated washed with 5% sodium hydrosulfite (3×), saturated sodium bicarbonate (3×), brine (3×) dried over anhydrous magnesium sulfate Removal of solvent