triphenyl phosphate

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a one-liter, stainless steel Parr autoclave vessel equipped for agitation, heating/cooling, and gas pressurization were charged 710 grams (2.29 moles) of triphenyl phosphite, 1.78 grams (0.0070 mole; 0.31 mole %) of iodine, and 2.34 grams (0.0144 mole; 0.63 mole %) of anhydrous iron (III) chloride. The mixture was heated to 115°-120° C. with efficient agitation and pressurized with oxygen at 55 psig. These conditions were maintained by applying sufficient cooling to control the accompanying exotherm which subsided after about 2.5 hours. The oxygenation was continued until no oxygen pressure drop was observed when the reaction vessel was isolated from the outside pressure line. The total reaction time was 5 hours. When the reaction vessel was vented, there was obtained 747 grams of triphenyl phosphate, an amber liquid that solidified upon cooling to room temperature. Gas chromatography showed the absence of triphenyl phosphite, thus demonstrating that the conversion of the phosphite to the phosphate was quantitative. heating/cooling The mixture was heated to 115°-120° C. with efficient agitation These conditions were maintained by applying sufficient cooling The oxygenation was isolated from the outside pressure line The total reaction time was 5 hours

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Placed in a 2000-mL flask equipped with a stirrer, dropping funnel and thermometer were 54.3 mg (0.15 mmol) of Cu(OTf)2, 25 g of toluene and 93.1 mg (0.30 mmol) of triphenyl phosphate, and the inner atmosphere was replaced with nitrogen. After replacement with nitrogen, the mixture was stirred at 25° C. for 20 min. Then, 9 mL (18 mmol) of a toluene solution (2.0 mmol/L) of dimethylzinc was added to the mixture at 25° C., followed by further stirring for 10 min. The mixture was then cooled to −17° C., followed by addition of 1.68 g (16.5 mmol) of acetic anhydride, and 3.34 g (15 mmol) of 2-cyclopentadecenone was added dropwise to the mixture over the period of 1 hour. After completion of the dropwise addition, stirring was continued at the same temperature for 6 hours. After the reaction was completed, 32.5 g of a 5% aqueous sulfuric acid solution as cooled to 0° C. was added to the reaction mixture for quenching. After separation, the organic layer was washed with water (5 times), and the resultant organic layer was concentrated under reduced pressure to give 4.93 g of a crude product. The crude product was purified by silica-gel column chromatography to produce 3.89 g (13.8 mmol, 92% yield) of dl-3-methycyclopentadecene-1-yl acetate. Placed in a 2000-mL flask equipped with a stirrer by further stirring for 10 min The mixture was then cooled to −17° C. was added dropwise to the mixture over the period of 1 hour After completion of the dropwise addition stirring was continued at the same temperature for 6 hours was added to the reaction mixture for quenching After separation the organic layer was washed with water (5 times) the resultant organic layer was concentrated under reduced pressure to give 4.93 g of a crude product The crude product was purified by silica-gel column chromatography

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Placed in a 2000-mL flask equipped with a stirrer, dropping funnel and thermometer were 54.3 mg (0.15 mmol) of Cu(OTf)2, 25 g of toluene and 93.1 mg (0.30 mmol) of triphenyl phosphate, and the inner atmosphere was replaced with nitrogen. After replacement with nitrogen, the mixture was stirred at 25° C. for 20 min. Then, 9 mL (18 mmol) of a toluene solution (2.0 mmol/L) of dimethylzinc was added to the mixture at 25° C., followed by further stirring for 10 min. The mixture was then cooled to −17° C., followed by addition of 1.68 g (16.5 mmol) of acetic anhydride, and 3.34 g (15 mmol) of 2-cyclopentadecenone was added dropwise to the mixture over the period of 1 hour. After completion of the dropwise addition, stirring was continued at the same temperature for 6 hours. After the reaction was completed, 32.5 g of a 5% aqueous sulfuric acid solution as cooled to 0° C. was added to the reaction mixture for quenching. After separation, the organic layer was washed with water (5 times), and the resultant organic layer was concentrated under reduced pressure to give 4.93 g of a crude product. The crude product was purified by silica-gel column chromatography to produce 3.89 g (13.8 mmol, 92% yield) of dl-3-methycyclopentadecene-1-yl acetate. Placed in a 2000-mL flask equipped with a stirrer by further stirring for 10 min The mixture was then cooled to −17° C. was added dropwise to the mixture over the period of 1 hour After completion of the dropwise addition stirring was continued at the same temperature for 6 hours was added to the reaction mixture for quenching After separation the organic layer was washed with water (5 times) the resultant organic layer was concentrated under reduced pressure to give 4.93 g of a crude product The crude product was purified by silica-gel column chromatography

反応条件: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of 1-(biphenyl-4-ylcarbonyl)piperidine-4-carboxylic acid (0.10 g, 0.32 mmol) and 3,4-diaminopyridine (35 mg, 0.32 mmol) in pyridine (1 mL) is added triphenyl phosphate (0.10 mL, 0.38 mmol). The mixture is heated under microwave irradiation at 120° C. for 50 mins. Purification by preparative HPLC gives 34 mg of biphenyl-4-yl[4-(1H-imidazo[4,5-c]pyridin-2-yl)piperidin-1-yl]methanone. Purification by preparative HPLC

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Prepare the title compound in a manner analogous to the procedure described in Scheme IIIa. For example, place ethyl 4-cyano-1-methyl-5-(trifluoromethyl)-3-{4-[(trifluoromethyl)sulfonyloxy]phenyl}pyrrole-2-carboxylate (11.0 mmol, prepared in example E-277), 2-cyano-phenyl boronic acid (1.5 mmol), palladium (II) acetate (0.12 mmol), triphenylphosphate (0.24 mmol), and tribasic potassium phosphate (3.6 mmol) in a round bottom flask and add dioxane. Heat reaction to reflux for 18 hours, remove the heat and wash with water while extracting with ethyl acetate. Dry organics with sodium sulfate, filter, and concentrate in vacuo. Purify the residue via radial chromatography eluting with methylene chloride, ethyl acetate and hexane to provide the title compound. Heat reaction to reflux for 18 hours remove the heat wash with water while extracting with ethyl acetate Dry organics with sodium sulfate, filter concentrate in vacuo Purify the residue via radial chromatography eluting with methylene chloride, ethyl acetate and hexane

反応条件: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 3-{2-[5-fluoro-3-(trifluoromethyl)phenyl]-1,3-oxazol-4-yl}propan-1-ol (250.3 mg, 0.865 mmol) was added a mixture of triphenyl phosphate (295.4 mg, 0.952 mmol, 1.1 equiv.) and methyl iodide (184.2 mg, 1.298 mmol, 1.5 equiv.). The mixture was heated at 130° C., while adding a further amount of methyl iodide (184.2 mg, 1.298 mmol, 1.5 equiv.). The reaction mixture was heated for a total of 2 hours, and then purified by column-chromatography (SiO2=25 g, hexane/EtOAc=7:1) followed by preparative TLC (SiO2=6 plates, hexane/EtOAc=15:1) to give 2-[5-fluoro-3-(trifluoromethyl)phenyl]-4-(3-iodopropyl)-1,3-oxazole (116.1 mg, 0.291 mmol, 34%) as a colorless oil. The reaction mixture was heated for a total of 2 hours purified by column-chromatography (SiO2=25 g, hexane/EtOAc=7:1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: (2S, 2S)-N-(2,4-Dimethoxy-benzyl)-N-(2-hydroxypropyl)-2-(2,2,2-trifluoroacetylamino)-propionamide (3.64 g, 9.29 mmol) is dissolved in 25 mL of tetrahydrofuran. Triphenylphosphate (3.65 g, 14.0 mmol) is added, and the resulting mixture is cooled to 0° C. before diethyl azodicarboxylate (2.2 mL, 14 mmol) is added slowly. The resulting mixture is left to stir overnight. The reaction mixture is condensed, and the residue is purified by column chromatography (SiO2, 25% ethyl acetate/hexane). The desired product, (3S, 5R)-1-(2,4-dimethoxy-benzyl)-3,5-dimethyl-4-trifluoroacetyl-piperazin-2-one (1.5 g, 43% yield), is isolated as a clear oil. is added slowly The resulting mixture is left condensed the residue is purified by column chromatography (SiO2, 25% ethyl acetate/hexane)