chloro(chlorosulfonyloxy)methane

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

Procedure: Decanoic acid (0.2 gm, 1.2 mmol) was treated with 4 eq NaHCO3, 0.1 eq Bu4NHSO4 and, 1.2 eq ClCH2OSO2Cl in 1:1 CH2Cl2:H2O. The reaction was stirred vigorously at 0° C. for 30 min then room temperature (“RT”) for 3 hrs. Aqueous workup yielded chloromethyldecanoate (yield 100%). room temperature (“RT”) for 3 hrs

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

Procedure: To a mixture of chloromethyl chlorosulfate (1.1 equivalent) and 4-tert-Butoxycarbonylamino-butyric acid (1 equivalent) was added NaHCO3 (3.6 equivalents) and Bu4NHSO4 (catalytic amount) in water/CH2Cl2 (1:1). The mixture was stirred at room temperature overnight. The organic phase was thereafter separated and the aqueous phase was extracted with CH2Cl2 (three times). The combined organic layer was washed with NaHCO3 (×3), brine (×3), dried with MgSO4, filtered and evaporated. The organic phase was thereafter separated the aqueous phase was extracted with CH2Cl2 (three times) The combined organic layer was washed with NaHCO3 (×3), brine (×3) dried with MgSO4 filtered evaporated

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

Procedure: Sodium bicarbonate (289 mg, 3.44 mmol) followed by tetrabutylammonium hydrogensulfate (29.2 mg, 0.086 mmol) were added to a vigorously stirred 0° C. mixture of methyl (3S,3aS,6R,6aS)-6-(nitrooxy)hexahydrofuro[3,2-b]furan-3-yl hydrogen phosphate (245 mg, 0.859 mmol) in dichloromethane (5 mL) and water (7.5 mL), and the mixture was stirred at 0° C. for 10 minutes. Chloromethyl chlorosulfate (0.106 mL, 1.03 mmol) in dichloromethane (2.5 mL) was added, and the mixture was stirred at room temperature for overnight. The organic phase was removed, dried and concentrated. Chromatography over silica, eluting with 20-60% ethyl acetate/hexane afforded the title compound as a colorless oil. 1H NMR (500 MHz, CDCl3) δ 5.72-5.64 (m, 2H), 5.36 (td, J=5.5, 2.8 Hz, 1H), 5.02 (t, J=5.2 Hz, 1H), 4.93 (quintet, J=3.6 Hz, 1H), 4.63 (dd, J=12.1, 4.8 Hz, 1H), 4.18 (dd, J=11.0, 7.3 Hz, 1H), 4.00 (dd, J=11.4, 2.8 Hz, 1H), 3.94 (dq, J=11.1, 2.4 Hz, 1H), 3.90 (dd, J=11.3, 5.6 Hz, 1H), 3,83 (d, J=11.4 Hz, 3H); LC-MS: m/z 334.0 (M+H). the mixture was stirred at room temperature for overnight The organic phase was removed dried concentrated Chromatography over silica, eluting with 20-60% ethyl acetate/hexane

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

Procedure: To a suspension of nicotinic acid (1.23 g, 0.01 mol) in a mixture of 10 mL of water and 20 mL of tetrahydrofuran were added tetrabutylammonium hydrogensulfate (0.34 g, 1 mmol) and sodium bicarbonate (3.19 g, 0.038 mol), with vigorous stirring. Chloromethyl chlorosulfate (1.81 g, 0.011 mol) in 5 mL of tetrahydrofuran was added dropwise, keeping the temperature below 30° C. The reaction mixture was stirred for 1 hour, then the layers were separated and the organic layer was dried by azeotroping with 1:1 acetonitrile/benzene. The residue was passed through a column of neutral alumina, eluting with chloroform. The chloroform layer was evaporated to give 1.28 g (74.8%) of an oily residue, which was confirmed by NMR analysis to have the structural formula: ##STR158## the temperature below 30° C the layers were separated the organic layer was dried by azeotroping with 1:1 acetonitrile/benzene eluting with chloroform The chloroform layer was evaporated

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

Procedure: To a well stirred suspension of di-tert-butyl hydrogen phosphate (4.7 g, 22.47 mmol) in water (186 ml) was added sodium bicarbonate (7.5 g, 89.52 mmol) followed by tetra-n-butylammomium hydrogen sulphate (760 mg, 2.238 mmol). The reaction mixture was stirred at room temperature for 15 min. To the reaction mixture was added dichloromethane (112 ml) at 0° C. and it was stirred for 10 min followed by the addition of chloromethyl chlorosulphate (4.4 g, 26.85 mmol) in dichloromethane (75 ml) at same temperature. The resultant mixture was vigorously stirred overnight at room temperature. The organic layer was separated, washed with brine and evaporated under reduced pressure to yield 3.04 g of product as pale yellow oil. The reaction mixture was stirred at room temperature for 15 min it was stirred for 10 min The organic layer was separated washed with brine evaporated under reduced pressure

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