Methyl 2-(oxetan-3-ylidene)acetate

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: Oxetan-3-one (commercially available) (50 mg, 0.69 mmol) was solved in 1 ml dichloromethane and cooled to 0-5° C. (Methoxycarbonylmethylene) triphenylphosphorane (255 mg, 0.76 mmol) was added and the mixture stirred for 15 minutes. The mixture was directly purified with column chromatography on silica gel using heptane:ethyl acetate 100:0->0:100. The product fractions were concentrated to give 57 mg (64% yield) of a white solid. was added The mixture was directly purified with column chromatography on silica gel The product fractions were concentrated

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

実験手順: Chlorotrimethylsilane (74 μl, 0.58 mmol) was solved in 1.5 ml THF. Copper(I) iodide (7 mg, 0.04 mmol) and oxetan-3-ylidene-acetic acid methyl ester (50 mg, 0.39 mmol) in 0.5 ml THF were added at room temperature and the mixture was stirred for 15 minutes at room temperature. The reaction mixture was cooled to −15° C. and 3N methylmagnesiumchloride-solution (0.52 ml, 1.56 mmol) was added drop wise. The reaction mixture was stirred for 1 hour at room temperature, quenched then with saturated NH4Cl-solution and extracted with dichloromethane. The organic extracts were washed with brine, dried with sodium sulfate, filtered and evaporated to give 65 mg (92%) light yellow oil. The crude product was used for the next step without further purification. The reaction mixture was cooled to −15° C. The reaction mixture was stirred for 1 hour at room temperature quenched with saturated NH4Cl-solution and extracted with dichloromethane The organic extracts were washed with brine dried with sodium sulfate filtered evaporated to give 65 mg (92%) light yellow oil The crude product was used for the next step without further purification

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

実験手順: Chlorotrimethylsilane (74 μl, 0.58 mmol) was solved in 1.5 ml THF. Copper(I) iodide (7 mg, 0.04 mmol) and oxetan-3-ylidene-acetic acid methyl ester (50 mg, 0.39 mmol) in 0.5 ml THF were added at room temperature and the mixture was stirred for 15 minutes at room temperature. The reaction mixture was cooled to −15° C. and 3N methylmagnesiumchloride-solution (0.52 ml, 1.56 mmol) was added drop wise. The reaction mixture was stirred for 1 hour at room temperature, quenched then with saturated NH4Cl-solution and extracted with dichloromethane. The organic extracts were washed with brine, dried with sodium sulfate, filtered and evaporated to give 65 mg (92%) light yellow oil. The crude product was used for the next step without further purification. The reaction mixture was cooled to −15° C. The reaction mixture was stirred for 1 hour at room temperature quenched with saturated NH4Cl-solution and extracted with dichloromethane The organic extracts were washed with brine dried with sodium sulfate filtered evaporated to give 65 mg (92%) light yellow oil The crude product was used for the next step without further purification

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

実験手順: Chlorotrimethylsilane (74 μl, 0.58 mmol) was solved in 1.5 ml THF. Copper(I) iodide (7 mg, 0.04 mmol) and oxetan-3-ylidene-acetic acid methyl ester (50 mg, 0.39 mmol) in 0.5 ml THF were added at room temperature and the mixture was stirred for 15 minutes at room temperature. The reaction mixture was cooled to −15° C. and 3N methylmagnesiumchloride-solution (0.52 ml, 1.56 mmol) was added drop wise. The reaction mixture was stirred for 1 hour at room temperature, quenched then with saturated NH4Cl-solution and extracted with dichloromethane. The organic extracts were washed with brine, dried with sodium sulfate, filtered and evaporated to give 65 mg (92%) light yellow oil. The crude product was used for the next step without further purification. The reaction mixture was cooled to −15° C. The reaction mixture was stirred for 1 hour at room temperature quenched with saturated NH4Cl-solution and extracted with dichloromethane The organic extracts were washed with brine dried with sodium sulfate filtered evaporated to give 65 mg (92%) light yellow oil The crude product was used for the next step without further purification

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

実験手順: Oxetan-3-one (commercially available) (50 mg, 0.69 mmol) was solved in 1 ml dichloromethane and cooled to 0-5° C. (Methoxycarbonylmethylene) triphenylphosphorane (255 mg, 0.76 mmol) was added and the mixture stirred for 15 minutes. The mixture was directly purified with column chromatography on silica gel using heptane:ethyl acetate 100:0->0:100. The product fractions were concentrated to give 57 mg (64% yield) of a white solid. was added The mixture was directly purified with column chromatography on silica gel The product fractions were concentrated

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

実験手順: Oxetan-3-one (commercially available) (50 mg, 0.69 mmol) was solved in 1 ml dichloromethane and cooled to 0-5° C. (Methoxycarbonylmethylene) triphenylphosphorane (255 mg, 0.76 mmol) was added and the mixture stirred for 15 minutes. The mixture was directly purified with column chromatography on silica gel using heptane:ethyl acetate 100:0->0:100. The product fractions were concentrated to give 57 mg (64% yield) of a white solid. was added The mixture was directly purified with column chromatography on silica gel The product fractions were concentrated

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

実験手順: Oxetan-3-ylidene-acetic acid methyl ester (Angewandte Chemie, International Edition (2006), 45(46), 7736-7739) ester (1.5 g; 11.72 mmol) in EtOH (20 ml) and liquid NH3 (11 g) are heated in a steel cylinder at 800 C for 5 hours. Evaporation of the solvent delivers the title compound as yellow resin. 1H-NMR (400 MHz; DMSO-d6): 4.42 (d, 2H); 4.34 (d, 2H); 3.61 (s, 3H); 2.77 (s, 2H); 2.33 (bs, 2H). MS (m/z) ES+: 145 (MH+; 15); 96 (100). Evaporation of the solvent