methyl (E)-3-cyclopropylprop-2-enoate

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

実験手順: To a solution of 68.2 g of potassium ferricyanide and 28.6 g of potassium carbonate in 640 ml of tert-butanol-water (1:1) is added 0.537 g of 1,4-bis(9-O-dihydroquinidyl)phthalazine. The pH of the reaction mixture is adjusted to pH 10.9 with aqueous solution of phosphoric acid. After a solution of osmium tetroxide in 0.35 ml of toluene (0.393M) is added to the mixture, the resulting mixture is stirred at room temperature for 30 minutes. Then, methyl trans-3-cyclopropylacrylate is added to the mixture, and the mixture is stirred for 24 hours. After the reaction mixture is cooled with ice, 106 g of sodium sulfite is added to the mixture. Then, the mixture is stirred for 30 minutes. The mixture is extracted with ethyl acetate four times. The organic layer is dried and the solvent is removed in vacuo. The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=3:l) to give 4.22 g of methyl (2S,3R)-3-cyclopropyl--2,3-dihydroxypropionate. the mixture is stirred for 24 hours is added to the mixture Then, the mixture is stirred for 30 minutes The mixture is extracted with ethyl acetate four times The organic layer is dried the solvent is removed in vacuo The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=3:l)

反応条件: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a suspension of 85.8 g of methoxycarbonylmethylenetriphenylphosphorane in 550 ml of benzene is added dropwise a solution of 15.0 g of cyclopropanecarbaldehyde in 50 ml of benzene at room temperature under argon atmosphere. The mixture is stirred at 55° C. overnight. After the reaction mixture is cooled to room temperature, the reaction mixture is poured into 800 ml of ice water. The aqueous mixture is extracted with 600 ml of chloroform twice. The chloroform layer is washed with brine. The organic layer is dried and evaporated under reduced pressure to remove the solvent. The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=12:1) to give 17.4 g of methyl trans-3-cyclopropylacrylate. After the reaction mixture is cooled to room temperature The aqueous mixture is extracted with 600 ml of chloroform twice The chloroform layer is washed with brine The organic layer is dried evaporated under reduced pressure to remove the solvent The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=12:1)

反応条件: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a suspension of 85.8 g of methoxycarbonylmethylenetriphenylphosphorane in 550 ml of benzene is added dropwise a solution of 15.0 g of cyclopropanecarbaldehyde in 50 ml of benzene at room temperature under argon atmosphere. The mixture is stirred at 55° C. overnight. After the reaction mixture is cooled to room temperature, the reaction mixture is poured into 800 ml of ice water. The aqueous mixture is extracted with 600 ml of chloroform twice. The chloroform layer is washed with brine. The organic layer is dried and evaporated under reduced pressure to remove the solvent. The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=12:1) to give 17.4 g of methyl trans-3-cyclopropylacrylate. After the reaction mixture is cooled to room temperature The aqueous mixture is extracted with 600 ml of chloroform twice The chloroform layer is washed with brine The organic layer is dried evaporated under reduced pressure to remove the solvent The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=12:1)

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

実験手順: (2)To a solution of 68.2 g of potassium ferricyanide and 28.6 g of potassium carbonate in 640 ml of tert-butanol-water (1:1) is added 0.537 g of 1,4-bis(9-O-dihydroquinidyl)phthalazine. The pH of the reaction mixture is adjusted to pH 10.9 with aqueous solution of phosphoric acid. After a solution of osmium tetroxide in 0.35 ml of toluene (0.393M) is added to the mixture, the resulting mixture is stirred at room temperature for 30 minutes. Then, methyl trans-3-cyclopropylacrylate is added to the mixture, and the mixture is stirred for 24 hours. After the reaction mixture is cooled with ice, 106 g of sodium sulfite is added to the mixture. Then, the mixture is stirred for 30 minutes. The mixture is extracted with ethyl acetate four times. The organic layer is dried and the solvent is removed in vacuo. The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=3:1) to give 4.22 g of methyl (2S,3R)-3-cyclopropyl-2,3-dihydroxypropionate. the mixture is stirred for 24 hours is added to the mixture Then, the mixture is stirred for 30 minutes The mixture is extracted with ethyl acetate four times The organic layer is dried the solvent is removed in vacuo The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=3:1)

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

実験手順: (2)To a solution of 68.2 g of potassium ferricyanide and 28.6 g of potassium carbonate in 640 ml of tert-butanol-water (1:1) is added 0.537 g of 1,4-bis(9-O-dihydroquinidyl)phthalazine. The pH of the reaction mixture is adjusted to pH 10.9 with aqueous solution of phosphoric acid. After a solution of osmium tetroxide in 0.35 ml of toluene (0.393M) is added to the mixture, the resulting mixture is stirred at room temperature for 30 minutes. Then, methyl trans-3-cyclopropylacrylate is added to the mixture, and the mixture is stirred for 24 hours. After the reaction mixture is cooled with ice, 106 g of sodium sulfite is added to the mixture. Then, the mixture is stirred for 30 minutes. The mixture is extracted with ethyl acetate four times. The organic layer is dried and the solvent is removed in vacuo. The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=3:1) to give 4.22 g of methyl (2S,3R)-3-cyclopropyl-2,3-dihydroxypropionate. the mixture is stirred for 24 hours is added to the mixture Then, the mixture is stirred for 30 minutes The mixture is extracted with ethyl acetate four times The organic layer is dried the solvent is removed in vacuo The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=3:1)

反応条件: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a suspension of 85.8 g of methoxycarbonylmethylenetriphenylphosphorane in 550 ml of benzene is added dropwise a solution of 15.0 g of cyclopropanecarbaldehyde in 50 ml of benzene at room temperature under argon atmosphere. The mixture is stirred at 55° C. overnight. After the reaction mixture is cooled to room temperature, the reaction mixture is poured into 800ml of ice water. The aqueous mixture is extracted with 600 ml of chloroform twice. The chloroform layer is washed with brine. The organic layer is dried and evaporated under reduced pressure to remove the solvent. The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=12:1) to give 17.4 g of methyl trans-3-cyclopropylacrylate. After the reaction mixture is cooled to room temperature The aqueous mixture is extracted with 600 ml of chloroform twice The chloroform layer is washed with brine The organic layer is dried evaporated under reduced pressure to remove the solvent The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=12:1)

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

実験手順: 101.1 To a stirred, cooled (0° C.) solution of 3.18 g N-benzyl-N-(methoxymethyl)trimethyl-silylmethylamine (CAS 93102-05-7) in 30 ml CH2Cl2 under an argon atmosphere was added dropwise a solution of 1.69 g (E)-3-cyclopropyl-acrylic acid methyl ester (CAS 59939-11-6; J. Org. Chem. 1990, 55(10), 3097) in 15 ml CH2Cl2 over a period of 20 min. Then a solution of 0.1 ml TFA in 5 ml CH2Cl2 was added dropwise within 10 min. When addition was complete, the mixture (slowly warming up to room temperature) was stirred overnight. Then, the mixture was diluted with CH2Cl2, washed with sat. aq. NaHCO3 and brine, dried over MgSO4, filtered and concentrated. The crude product was isolated by chromatography (silica gel; (gradient: cyclohexane->cyclohexane/EtOAc 7:3) to give 1.14 g (3RS,4RS)-1-benzyl-4-cyclopropyl-pyrrolidine-3-carboxylic acid methyl ester as light yellow oil. MS 260.3 ([M+H]+) When addition washed with sat. aq. NaHCO3 and brine dried over MgSO4 filtered concentrated The crude product was isolated by chromatography (silica gel

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

実験手順: To a solution of 68.2 g of potassium ferricyanide and 28.6 g of potassium carbonate in 640 ml of tert-butanol-water (1:1) is added 0.537 g of 1,4-bis(9-O-dihydroquinidyl)phthalazine. The pH of the reaction mixture is adjusted to pH 10.9 with aqueous solution of phosphoric acid. After a solution of osmium tetroxide in 0.35 ml of toluene (0.393M) is added to the mixture, the resulting mixture is stirred at room temperature for 30 minutes. Then, methyl trans-3-cyclopropylacrylate is added to the mixture, and the mixture is stirred for 24 hours. After the reaction mixture is cooled with ice, 106 g of sodium sulfite is added to the mixture. Then, the mixture is stirred for 30 minutes. The mixture is extracted with ethyl acetate four times. The organic layer is dried and the solvent is removed in vacuo. The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=3:l) to give 4.22 g of methyl (2S,3R)-3-cyclopropyl--2,3-dihydroxypropionate. the mixture is stirred for 24 hours is added to the mixture Then, the mixture is stirred for 30 minutes The mixture is extracted with ethyl acetate four times The organic layer is dried the solvent is removed in vacuo The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=3:l)

反応条件: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a suspension of 85.8 g of methoxycarbonylmethylenetriphenylphosphorane in 550 ml of benzene is added dropwise a solution of 15.0 g of cyclopropanecarbaldehyde in 50 ml of benzene at room temperature under argon atmosphere. The mixture is stirred at 55° C. overnight. After the reaction mixture is cooled to room temperature, the reaction mixture is poured into 800 ml of ice water. The aqueous mixture is extracted with 600 ml of chloroform twice. The chloroform layer is washed with brine. The organic layer is dried and evaporated under reduced pressure to remove the solvent. The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=12:1) to give 17.4 g of methyl trans-3-cyclopropylacrylate. After the reaction mixture is cooled to room temperature The aqueous mixture is extracted with 600 ml of chloroform twice The chloroform layer is washed with brine The organic layer is dried evaporated under reduced pressure to remove the solvent The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=12:1)

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

実験手順: (2)To a solution of 68.2 g of potassium ferricyanide and 28.6 g of potassium carbonate in 640 ml of tert-butanol-water (1:1) is added 0.537 g of 1,4-bis(9-O-dihydroquinidyl)phthalazine. The pH of the reaction mixture is adjusted to pH 10.9 with aqueous solution of phosphoric acid. After a solution of osmium tetroxide in 0.35 ml of toluene (0.393M) is added to the mixture, the resulting mixture is stirred at room temperature for 30 minutes. Then, methyl trans-3-cyclopropylacrylate is added to the mixture, and the mixture is stirred for 24 hours. After the reaction mixture is cooled with ice, 106 g of sodium sulfite is added to the mixture. Then, the mixture is stirred for 30 minutes. The mixture is extracted with ethyl acetate four times. The organic layer is dried and the solvent is removed in vacuo. The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=3:1) to give 4.22 g of methyl (2S,3R)-3-cyclopropyl-2,3-dihydroxypropionate. the mixture is stirred for 24 hours is added to the mixture Then, the mixture is stirred for 30 minutes The mixture is extracted with ethyl acetate four times The organic layer is dried the solvent is removed in vacuo The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=3:1)

反応条件: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a suspension of 85.8 g of methoxycarbonylmethylenetriphenylphosphorane in 550 ml of benzene is added dropwise a solution of 15.0 g of cyclopropanecarbaldehyde in 50 ml of benzene at room temperature under argon atmosphere. The mixture is stirred at 55° C. overnight. After the reaction mixture is cooled to room temperature, the reaction mixture is poured into 800ml of ice water. The aqueous mixture is extracted with 600 ml of chloroform twice. The chloroform layer is washed with brine. The organic layer is dried and evaporated under reduced pressure to remove the solvent. The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=12:1) to give 17.4 g of methyl trans-3-cyclopropylacrylate. After the reaction mixture is cooled to room temperature The aqueous mixture is extracted with 600 ml of chloroform twice The chloroform layer is washed with brine The organic layer is dried evaporated under reduced pressure to remove the solvent The residue is purified by silica gel column chromatography (solvent; hexane:ethyl acetate=12:1)