trimethyl(methylsulfanyl)silane

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

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

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 3,5-dinitroanisole (5.0 g, 25.23 mmol) in dimethylsulfoxide (50 mL) were added methylthiotrimethylsilane (4.86 g, 40.37 mmol) and cesium carbonate (16.61 g, 50.46 mmol) at room temperature. The resulting dark green solution was stirred for 15 h at this temperature. Then, the reaction mixture was heated to 90° C. and the resulting brown mixture was stirred for another 5 h at which time TLC analysis of the mixture indicated the absence of starting material. The reaction mixture was cooled to room temperature and diluted with water (100 mL) and ethyl acetate (100 mL). The two layers were separated and the aqueous layer was extracted with ethyl acetate (50 mL). The combined extracts were washed with brine solution (150 mL) and dried over anhydrous magnesium sulfate. Filtration of the drying agent and the concentration of the solution under vacuum gave the crude residue which was purified by using an ISCO 120 column chromatography, eluting with 0-20% ethyl acetate in hexanes to obtain 1-methoxy-3-methylsulfanyl-5-nitro-benzene (1.44 g, 28.6%) as an yellow solid: EI(+)-HRMS m/e calcd for C8H9NO3S (M)+ 199.0303, found 199.0294. the resulting brown mixture was stirred for another 5 h at which time TLC analysis of the mixture The reaction mixture was cooled to room temperature The two layers were separated the aqueous layer was extracted with ethyl acetate (50 mL) The combined extracts were washed with brine solution (150 mL) dried over anhydrous magnesium sulfate Filtration of the drying agent the concentration of the solution under vacuum gave the crude residue which was purified eluting with 0-20% ethyl acetate in hexanes

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

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 3,5-dinitroanisole (5.0 g, 25.23 mmol) in dimethylsulfoxide (50 mL) were added methylthiotrimethylsilane (4.86 g, 40.37 mmol) and cesium carbonate (16.61 g, 50.46 mmol) at room temperature. The resulting dark green solution was stirred for 15 h at this temperature. Then, the reaction mixture was heated to 90° C. and the resulting brown mixture was stirred for another 5 h at which time TLC analysis of the mixture indicated the absence of starting material. The reaction mixture was cooled to room temperature and diluted with water (100 mL) and ethyl acetate (100 mL). The two layers were separated and the aqueous layer was extracted with ethyl acetate (50 mL). The combined extracts were washed with brine solution (150 mL) and dried over anhydrous magnesium sulfate. Filtration of the drying agent and the concentration of the solution under vacuum gave the crude residue which was purified by using an ISCO 120 column chromatography, eluting with 0-20% ethyl acetate in hexanes to obtain 1-methoxy-3-methylsulfanyl-5-nitro-benzene (1.44 g, 28.6%) as an yellow solid: EI(+)-HRMS m/e calcd for C8H9NO3S (M)+ 199.0303, found 199.0294. the resulting brown mixture was stirred for another 5 h at which time TLC analysis of the mixture The reaction mixture was cooled to room temperature The two layers were separated the aqueous layer was extracted with ethyl acetate (50 mL) The combined extracts were washed with brine solution (150 mL) dried over anhydrous magnesium sulfate Filtration of the drying agent the concentration of the solution under vacuum gave the crude residue which was purified eluting with 0-20% ethyl acetate in hexanes

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

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

Procedure: A mixture of 1,3,4,6-tetra-O-acetyl-2-deoxy-2-phthalimido-β-D-galactose (680 mg, 1.425 mmol), methylthiotrimethylsilane (0.8 ml, 5.64 mmol), and trimethyl silyl triflate (0.32 ml, 1.66 mmol) in CH2Cl2 was stirred at room temperature for 2 days. Diisopropylamine (~1 ml) was added, diluted with CH2Cl2 (~50 ml) and washed with saturated NaHCO3 solution and water, respectively. The organic layer was dried (Na2SO4) and evaporated to dryness. Column chromatography (heptane-EtOAc) gave pure 20 (630 mg, 95%) as an amorphous powder, having [α]D24 +25° (c1, CHCl3). washed with saturated NaHCO3 solution and water The organic layer was dried (Na2SO4) evaporated to dryness

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1,2,3,5,6-Penta-O-propanoyl-β-D-glucofuranose (614 mg, 1.3 mmol) was dissolved in 1,2-dichloroethane (5 mL) and cooled to 0° C. (Methylthio)trimethylsilane (567 μL, 4.0 mmol) was added dropwise followed by trimethylsilyl trifluoromethanesulfonate (72 μL, 0.4 mmol). After 20 min at room temperature, the mixture was heated at 50° C. for 3 h, cooled, diluted with CHCl3, washed with 50% aqueous NaHCO3 (30 mL), brine, dried (MgSO4) and concentrated in vacuo. Flash silica chromatography of the residue, eluting with 10% ethyl acetate in petroleum ether, gave methyl 2,3,5,6-tetra-O-propanoyl-1-thio-β-D-glucofuranoside as a colourless solid (470 mg, 81%). A sample was recrystallised from ethanol to give colourless needles, mp 62-63° C. (from EtOH), [α]D22=−50.5 (c 1.0 in CHCl3), (Found: C, 52.7; H, 7.2; S, 7.4. C19H30O9S requires C, 52.5; H, 7.0; S 7.4%); δH (CDCl3) 5.37 (1H, d, J 4.2, 3-H), 5.33 (1H, ddd, J 9.3, 5.1 and 2.5, 5-H), 5.07 (1H, d, J 2.2, 2-H), 5.00 (1H, d, J 2.2, 1-H), 4.62 (1H, dd, J 12.3 and 5.1, 2.5, 6a-H), 4.36 (1H, dd, J 9.3 and 4.2, 4-H), 4.17 (1H, dd, J 12.3 and 5.1, 6b-H), 2.39 (2H, q, J 7.6, CH2), 2.37 (2H, q, J 7.6, CH2), 2.35 (2H, q, J 7.6, CH2), 2.26 (2H, q, J 7.6, CH2), 2.23 (3H, s, SCH3) 1.16 (3H, t, J 7.6, CH3), 1.14 (3H, t, J 7.6, CH3), 1.13 (3H, t, J 7.6, CH3), 1.09 (3H, t, J 7.6, CH3); δC (CDCl3) 174.4, 173.3, 173.1, 173.1 (4×C═O), 89.6 (1-C), 81.6 (2-C), 79.1 (4-C), 74.7 (3-C), 68.4 (5-C), 63.4 (6-C), 27.7 (4×CH2), 9.4, 9.2, 9.2, 9.1 (4×CH3); m/z (FAB) 435.169691 (MH+, C19H31O9S requires 435.168880). was added dropwise cooled washed with 50% aqueous NaHCO3 (30 mL), brine dried (MgSO4) concentrated in vacuo Flash silica chromatography of the residue, eluting with 10% ethyl acetate in petroleum ether

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 3,5-dinitroanisole (5.0 g, 25.23 mmol) in dimethylsulfoxide (50 mL) were added methylthiotrimethylsilane (4.86 g, 40.37 mmol) and cesium carbonate (16.61 g, 50.46 mmol) at room temperature. The resulting dark green solution was stirred for 15 h at this temperature. Then, the reaction mixture was heated to 90° C. and the resulting brown mixture was stirred for another 5 h at which time TLC analysis of the mixture indicated the absence of starting material. The reaction mixture was cooled to room temperature and diluted with water (100 mL) and ethyl acetate (100 mL). The two layers were separated and the aqueous layer was extracted with ethyl acetate (50 mL). The combined extracts were washed with brine solution (150 mL) and dried over anhydrous magnesium sulfate. Filtration of the drying agent and the concentration of the solution under vacuum gave the crude residue which was purified by using an ISCO 120 column chromatography, eluting with 0-20% ethyl acetate in hexanes to obtain 1-methoxy-3-methylsulfanyl-5-nitro-benzene (1.44 g, 28.6%) as an yellow solid: EI(+)-HRMS m/e calcd for C8H9NO3S (M)+ 199.0303, found 199.0294. the resulting brown mixture was stirred for another 5 h at which time TLC analysis of the mixture The reaction mixture was cooled to room temperature The two layers were separated the aqueous layer was extracted with ethyl acetate (50 mL) The combined extracts were washed with brine solution (150 mL) dried over anhydrous magnesium sulfate Filtration of the drying agent the concentration of the solution under vacuum gave the crude residue which was purified eluting with 0-20% ethyl acetate in hexanes