trimethyl(1,1,2,2,2-pentafluoroethyl)silane

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

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

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flask charged with 4-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranos-1-yl)-2-(4-iodo-benzyl)-benzonitrile (0.16 g), pentafluoroethyltrimethylsilane (0.14 g), KF (43 mg), CuI (0.16 g), DMF (2 mL) and Ar atmosphere is heated at 60° C. for 24 h. Then, aqueous NaHCO3 solution is added and the resulting mixture is extracted with ethyl acetate. The combined organic phases are dried over sodium sulfate and the solvent is removed. The residue is dissolved in methanol (8 mL) and treated with 4 M KOH solution (0.8 mL). The solution is stirred at room temperature for 1 h and then diluted with aqueous NaHCO3 solution. After removal of the methanol under reduced pressure, the residue is extracted with ethyl acetate, the combined organic extracts are dried and the solvent is removed. The residue is chromatographed on silica gel (dichloromethane/methanol 1:0->8:1). the resulting mixture is extracted with ethyl acetate The combined organic phases are dried over sodium sulfate the solvent is removed The residue is dissolved in methanol (8 mL) treated with 4 M KOH solution (0.8 mL) diluted with aqueous NaHCO3 solution After removal of the methanol under reduced pressure the residue is extracted with ethyl acetate the combined organic extracts are dried the solvent is removed The residue is chromatographed on silica gel (dichloromethane/methanol 1:0->8:1)

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flask charged with 4-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranos-1-yl)-2-(4-iodo-benzyl)-benzonitrile (0.16 g), pentafluoroethyltrimethylsilane (0.14 g), KF (43 mg), CuI (0.16 g), DMF (2 mL) and Ar atmosphere is heated at 60° C. for 24 h. Then, aqueous NaHCO3 solution is added and the resulting mixture is extracted with ethyl acetate. The combined organic phases are dried over sodium sulfate and the solvent is removed. The residue is dissolved in methanol (8 mL) and treated with 4 M KOH solution (0.8 mL). The solution is stirred at room temperature for 1 h and then diluted with aqueous NaHCO3 solution. After removal of the methanol under reduced pressure, the residue is extracted with ethyl acetate, the combined organic extracts are dried and the solvent is removed. The residue is chromatographed on silica gel (dichloromethane/methanol 1:0->8:1). the resulting mixture is extracted with ethyl acetate The combined organic phases are dried over sodium sulfate the solvent is removed The residue is dissolved in methanol (8 mL) treated with 4 M KOH solution (0.8 mL) diluted with aqueous NaHCO3 solution After removal of the methanol under reduced pressure the residue is extracted with ethyl acetate the combined organic extracts are dried the solvent is removed The residue is chromatographed on silica gel (dichloromethane/methanol 1:0->8:1)

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2.00 g 4-iodo-anisol, 2.00 g pentafluoroethyl-trimethylsilane, 0.60 g potassium fluoride, 2.43 g copper iodide and 15 ml N,N-dimethylformamide is stirred overnight at 80° C. Then the mixture is stirred for a further 36 h at 80° C., while a further 2.00 g pentafluoroethyl-trimethylsilane are added after 4 h, 12 h and 24 h. After cooling to ambient temperature 2 M aqueous ammonia solution is added and the mixture is filtered. The filtrate is extracted with ethyl acetate, and the combined organic extracts are dried (Na2SO4) and evaporated down. The residue is chromatographed on silica gel with petroleum ether/ethyl acetate (9:1) as eluant. are added after 4 h, 12 h and 24 h is added the mixture is filtered The filtrate is extracted with ethyl acetate the combined organic extracts are dried (Na2SO4) evaporated down The residue is chromatographed on silica gel with petroleum ether/ethyl acetate (9:1) as eluant

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

Procedure: To a solution of methyl 4-acetylbenzoate (700 mg, 3.85 mmol) in tetrahydrofuran (7.7 mL) were added (pentafluoroethyl)trimethylsilane (1370 mg, 6.93 mmol) and tetrabutylammonium fluoride (tetrahydrofuran solution, 1 mol/L, 5.7 μL, 5.78 mmol) at 0° C., and the mixture was stirred at room temperature overnight. To the solution was added 1 mol/L hydrochloric acid solution, and the mixture was extracted with ethyl acetate three times. The organic layer was combined, filtered through Phase-separator (Varian Inc.), and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=100:0→70:30) to give methyl 4-(2,2,3,3,3-pentafluoro-1-hydroxy-1-methylpropyl)benzoate (765 mg, 67%) as a pale yellow viscous material. the mixture was extracted with ethyl acetate three times filtered through Phase-separator (Varian Inc.) concentrated under reduced pressure The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=100:0→70:30)

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

Procedure: To a solution of methyl 4-acetylbenzoate (700 mg, 3.85 mmol) in tetrahydrofuran (7.7 mL) were added (pentafluoroethyl)trimethylsilane (1370 mg, 6.93 mmol) and tetrabutylammonium fluoride (tetrahydrofuran solution, 1 mol/L, 5.7 μL, 5.78 mmol) at 0° C., and the mixture was stirred at room temperature overnight. To the solution was added 1 mol/L hydrochloric acid solution, and the mixture was extracted with ethyl acetate three times. The organic layer was combined, filtered through Phase-separator (Varian Inc.), and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=100:0→70:30) to give methyl 4-(2,2,3,3,3-pentafluoro-1-hydroxy-1-methylpropyl)benzoate (765 mg, 67%) as a pale yellow viscous material. the mixture was extracted with ethyl acetate three times filtered through Phase-separator (Varian Inc.) concentrated under reduced pressure The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=100:0→70:30)

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under argon in a microwave vial 2 g 1-bromo-4-iodobenzene, 3.3 g trimethyl(perfluoroethyl)silane, 493 mg potassium fluoride and 2 g copper iodide are suspended in 10 ml N,N-dimethylformamide. The mixture is heated for 12 hours at 80° C. Further 3.3 g trimethyl(perfluoroethyl)silane are added and heating is continued for 48 hours. Then the mixture is partitioned between 2 M ammonia and diethylether. The aqueous phase is twice extracted with diethylether. The combined organic phases are washed three times with water and dried with magnesium sulphate. The solvent is evaporated in vacuo (300 mbar, temperature of water bath 50° C.). The residue is chromatographed on silica gel (dichloromethane). heating Then the mixture is partitioned between 2 M ammonia and diethylether The aqueous phase is twice extracted with diethylether The combined organic phases are washed three times with water dried with magnesium sulphate The solvent is evaporated in vacuo (300 mbar, temperature of water bath 50° C.) The residue is chromatographed on silica gel (dichloromethane)

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flask charged with 4-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranos-1-yl)-2-(4-iodo-benzyl)-benzonitrile (0.16 g), pentafluoroethyltrimethylsilane (0.14 g), KF (43 mg), CuI (0.16 g), DMF (2 mL) and Ar atmosphere is heated at 60° C. for 24 h. Then, aqueous NaHCO3 solution is added and the resulting mixture is extracted with ethyl acetate. The combined organic phases are dried over sodium sulfate and the solvent is removed. The residue is dissolved in methanol (8 mL) and treated with 4 M KOH solution (0.8 mL). The solution is stirred at room temperature for 1 h and then diluted with aqueous NaHCO3 solution. After removal of the methanol under reduced pressure, the residue is extracted with ethyl acetate, the combined organic extracts are dried and the solvent is removed. The residue is chromatographed on silica gel (dichloromethane/methanol 1:0->8:1). the resulting mixture is extracted with ethyl acetate The combined organic phases are dried over sodium sulfate the solvent is removed The residue is dissolved in methanol (8 mL) treated with 4 M KOH solution (0.8 mL) diluted with aqueous NaHCO3 solution After removal of the methanol under reduced pressure the residue is extracted with ethyl acetate the combined organic extracts are dried the solvent is removed The residue is chromatographed on silica gel (dichloromethane/methanol 1:0->8:1)

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

Procedure: 13.2 g (91.9 mmol) of copper(I) bromide were cooled to −5° C. in 80 ml of dry N,N-dimethylformamide. Under nitrogen, 14.7 g (76.7 mmol) of trimethyl-(pentafluoroethyl)silane were added. 4.45 g (76.7 mmol) of potassium fluoride (spray-dried) were added in portions over the course of 30 minutes at a rate such that the internal temperature remained below 0° C. The mixture was stirred at 0° C. for 1 hour and was then warmed to 20° C. over the course of 12 hours. Thereafter 10 ml of dry 1,3-dimethyl-2-imidazolidinone and 22 g (73.1 mmol) of 3-fluoro-4-iodo-bromobenzene were added. The contents were stirred at 75° C. for 14 hours. Then all of the volatile constituents were distilled off to dryness, the distillate being collected in a cold trap cooled with liquid nitrogen. The distillate was subsequently warmed to 20° C. and dissolved in 500 ml of diethyl ether. This solution was washed with four times 100 ml of water and then with two times 100 ml of saturated aqueous NaCl solution. The organic phase was then dried, and the solvent was removed on a Vigreux column. Subsequent distillation of the residue on a Vigreux column gave 16.1 g of product (boiling point: 86-87° C. (75 mmHg)) with a purity of 99% by weight. remained below 0° C was then warmed to 20° C. over the course of 12 hours The contents were stirred at 75° C. for 14 hours Then all of the volatile constituents were distilled off to dryness the distillate being collected in a cold trap cooled with liquid nitrogen The distillate was subsequently warmed to 20° C. dissolved in 500 ml of diethyl ether This solution was washed with four times 100 ml of water The organic phase was then dried the solvent was removed on a Vigreux column Subsequent distillation of the residue on a Vigreux column

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flask charged with 4-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranos-1-yl)-2-(4-iodo-benzyl)-benzonitrile (0.16 g), pentafluoroethyltrimethylsilane (0.14 g), KF (43 mg), CuI (0.16 g), DMF (2 mL) and Ar atmosphere is heated at 60° C. for 24 h. Then, aqueous NaHCO3 solution is added and the resulting mixture is extracted with ethyl acetate. The combined organic phases are dried over sodium sulfate and the solvent is removed. The residue is dissolved in methanol (8 mL) and treated with 4 M KOH solution (0.8 mL). The solution is stirred at room temperature for 1 h and then diluted with aqueous NaHCO3 solution. After removal of the methanol under reduced pressure, the residue is extracted with ethyl acetate, the combined organic extracts are dried and the solvent is removed. The residue is chromatographed on silica gel (dichloromethane/methanol 1:0->8:1). the resulting mixture is extracted with ethyl acetate The combined organic phases are dried over sodium sulfate the solvent is removed The residue is dissolved in methanol (8 mL) treated with 4 M KOH solution (0.8 mL) diluted with aqueous NaHCO3 solution After removal of the methanol under reduced pressure the residue is extracted with ethyl acetate the combined organic extracts are dried the solvent is removed The residue is chromatographed on silica gel (dichloromethane/methanol 1:0->8:1)

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