ethyl 2-(oxetan-3-ylidene)acetate

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

実験手順: To a solution of [Rh(cod)C1]2 (171.3 mg, 0.3518 mmol) in 30 mL of dioxane was added aqueous KOH (6.097 mL of 1.5 M, 9.145 mmol) followed by ethyl 2-(oxetan-3-ylidene)acetate (1 g, 7.035 mmol) and a solution of (3-bromophenyl)boronic acid (2.119 g, 10.55 mmol) in 10 mL of dioxane. The reaction was stirred for 30 minutes at room temperature then further (3-bromophenyl)boronic acid (706 mg, 0.5 eq) was added and the reaction stirred overnight. Brine was added and the aqueous layer extracted twice with ethyl acetate. The combined organics were washed with brine and then dried, filtered and concentrated under reduced pressure. The crude product was purified on silica (Companion, 80 g) eluting with 1-20% EtOAc:Petrol ether to give ethyl 2-[3-(3-bromophenyl)oxetan-3-yl]acetate as a yellow oil (1.50 g, 71%). the reaction stirred overnight the aqueous layer extracted twice with ethyl acetate The combined organics were washed with brine dried filtered concentrated under reduced pressure The crude product was purified on silica (Companion, 80 g) eluting with 1-20% EtOAc

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

実験手順: To a solution of oxetan-3-one (500 mg, 6.938 mmol) in DCM (15.00 mL) at 0° C. was added ethyl 2-triphenylphosphoranylideneacetate (2.659 g, 7.632 mmol). The solution was allowed to warm to room temperature and stirred for 15 minutes. The reaction mixture was then filtered through a pad of silica (washing with 30% EtOAc:Petrol ether), and the solvent removed under reduced pressure to give ethyl 2-(oxetan-3-ylidene)acetate as a colourless viscous oil (815 mg, 79%). The reaction mixture was then filtered through a pad of silica (washing with 30% EtOAc:Petrol ether) the solvent removed under reduced pressure

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

実験手順: To a solution of [Rh(cod)C1]2 (171.3 mg, 0.3518 mmol) in 30 mL of dioxane was added aqueous KOH (6.097 mL of 1.5 M, 9.145 mmol) followed by ethyl 2-(oxetan-3-ylidene)acetate (1 g, 7.035 mmol) and a solution of (3-bromophenyl)boronic acid (2.119 g, 10.55 mmol) in 10 mL of dioxane. The reaction was stirred for 30 minutes at room temperature then further (3-bromophenyl)boronic acid (706 mg, 0.5 eq) was added and the reaction stirred overnight. Brine was added and the aqueous layer extracted twice with ethyl acetate. The combined organics were washed with brine and then dried, filtered and concentrated under reduced pressure. The crude product was purified on silica (Companion, 80 g) eluting with 1-20% EtOAc:Petrol ether to give ethyl 2-[3-(3-bromophenyl)oxetan-3-yl]acetate as a yellow oil (1.50 g, 71%). the reaction stirred overnight the aqueous layer extracted twice with ethyl acetate The combined organics were washed with brine dried filtered concentrated under reduced pressure The crude product was purified on silica (Companion, 80 g) eluting with 1-20% EtOAc

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

実験手順: To a solution of oxetan-3-one (500 mg, 6.938 mmol) in DCM (15.00 mL) at 0° C. was added ethyl 2-triphenylphosphoranylideneacetate (2.659 g, 7.632 mmol). The solution was allowed to warm to room temperature and stirred for 15 minutes. The reaction mixture was then filtered through a pad of silica (washing with 30% EtOAc:Petrol ether), and the solvent removed under reduced pressure to give ethyl 2-(oxetan-3-ylidene)acetate as a colourless viscous oil (815 mg, 79%). The reaction mixture was then filtered through a pad of silica (washing with 30% EtOAc:Petrol ether) the solvent removed under reduced pressure

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

実験手順: To a solution of [Rh(cod)Cl]2 (171.3 mg, 0.3518 mmol) in 30 mL of dioxane was added aqueous KOH (6.097 mL of 1.5 M, 9.145 mmol) followed by ethyl 2-(oxetan-3-ylidene)acetate (1 g, 7.035 mmol) and a solution of (3-bromophenyl)boronic acid (2.119 g, 10.55 mmol) in 10 mL of dioxane. The reaction was stirred for 30 minutes at room temperature then further (3-bromophenyl)boronic acid (706 mg, 0.5 eq) was added and the reaction stirred overnight. Brine was added and the aqueous layer extracted twice with ethyl acetate. The combined organics were washed with brine and then dried, filtered and concentrated under reduced pressure. The crude product was purified on silica (Companion, 80 g) eluting with 1-20% EtOAc:Petrol ether to give ethyl 2-[3-(3-bromophenyl)oxetan-3-yl]acetate as a yellow oil (1.50 g, 71%). the reaction stirred overnight the aqueous layer extracted twice with ethyl acetate The combined organics were washed with brine dried filtered concentrated under reduced pressure The crude product was purified on silica (Companion, 80 g) eluting with 1-20% EtOAc

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

実験手順: To a solution of oxetan-3-one (500 mg, 6.938 mmol) in DCM (15.00 mL) at 0° C. was added ethyl 2-triphenylphosphoranylideneacetate (2.659 g, 7.632 mmol). The solution was allowed to warm to room temperature and stirred for 15 minutes. The reaction mixture was then filtered through a pad of silica (washing with 30% EtOAc:Petrol ether). and the solvent removed under reduced pressure to give ethyl 2-(oxetan-3-ylidene)acetate as a colourless viscous oil (815 mg, 79%). The reaction mixture was then filtered through a pad of silica (washing with 30% EtOAc:Petrol ether) and the solvent removed under reduced pressure

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

実験手順: To a solution of oxetan-3-one (118) (5 g, 69.4 mmol) in CH2Cl2 (50 mL) at 0° C. was added ethyl 2-triphenylphosphoranylideneacetate (119) (26.6 g, 76.3 mmol). The solution was allowed to warm to RT and stirred for 15 min. The reaction mixture was then filtered through a pad of silica (washing with 30 percent EtOAc:Petrol ether), and the solvent removed under reduced pressure to give ethyl 2-(oxetan-3-ylidene)acetate (120) as a colourless viscous oil (8.15 g, 57.4 mmol, yield: 79%). ESI-MS (M+1): 142 calc. for C7H10O3 142. The reaction mixture was then filtered through a pad of silica (washing with 30 percent EtOAc:Petrol ether) the solvent removed under reduced pressure

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

実験手順: To a solution of (carbethoxymethylene)triphenylphosphorane (1.95 Kg, 5.61 mol) in dichloromethane (4 L) at 0° C. was added over 1 hour, a solution of 3-oxetanone (400 g, 5.55 mol) in dichloromethane (2 L) maintaining the temperature below 10° C. The reaction was warmed gradually to room temperature and stirred for 1.5 hours. The reaction was warmed to 30° C. and dichloromethane (˜4 L) removed in vacuo. Heptane (5 L) was added and the mixture distilled under vacuum for a further 1 hour. Further heptane (2.5 L) was added, the temperature increased to 50° C. and the reaction continued to be distilled under vacuum for a further 2 hours. The mixture was cooled to 0° C. and aged for 1 hour at atmospheric pressure. The solid was collected by filtration and washed with heptane (2×2.5 L). The pale yellow filtrate was concentrated in vacuo to afford the title compound as a pale yellow mobile liquid (757 g, 96% yield). The reaction was warmed to 30° C. dichloromethane (˜4 L) removed in vacuo Heptane (5 L) was added the mixture distilled under vacuum for a further 1 hour Further heptane (2.5 L) was added the temperature increased to 50° C. to be distilled under vacuum for a further 2 hours The mixture was cooled to 0° C. aged for 1 hour at atmospheric pressure The solid was collected by filtration washed with heptane (2×2.5 L) The pale yellow filtrate was concentrated in vacuo

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Ethyl oxetan-3-ylideneacetate (Preparation 38, 781 g, 5.49 mol) was dissolved in 2M ammonia in ethanol (8.24 L) and heated to 100° C. in a bomb for 5 hours. The reaction was concentrated in vacuo to afford the title compound as a mobile oil (750 g, 100% yield). The reaction was concentrated in vacuo

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

実験手順: To a solution of [Rh(cod)C1]2 (171.3 mg, 0.3518 mmol) in 30 mL of dioxane was added aqueous KOH (6.097 mL of 1.5 M, 9.145 mmol) followed by ethyl 2-(oxetan-3-ylidene)acetate (1 g, 7.035 mmol) and a solution of (3-bromophenyl)boronic acid (2.119 g, 10.55 mmol) in 10 mL of dioxane. The reaction was stirred for 30 minutes at room temperature then further (3-bromophenyl)boronic acid (706 mg, 0.5 eq) was added and the reaction stirred overnight. Brine was added and the aqueous layer extracted twice with ethyl acetate. The combined organics were washed with brine and then dried, filtered and concentrated under reduced pressure. The crude product was purified on silica (Companion, 80 g) eluting with 1-20% EtOAc:Petrol ether to give ethyl 2-[3-(3-bromophenyl)oxetan-3-yl]acetate as a yellow oil (1.50 g, 71%). the reaction stirred overnight the aqueous layer extracted twice with ethyl acetate The combined organics were washed with brine dried filtered concentrated under reduced pressure The crude product was purified on silica (Companion, 80 g) eluting with 1-20% EtOAc

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

実験手順: To a solution of oxetan-3-one (500 mg, 6.938 mmol) in DCM (15.00 mL) at 0° C. was added ethyl 2-triphenylphosphoranylideneacetate (2.659 g, 7.632 mmol). The solution was allowed to warm to room temperature and stirred for 15 minutes. The reaction mixture was then filtered through a pad of silica (washing with 30% EtOAc:Petrol ether), and the solvent removed under reduced pressure to give ethyl 2-(oxetan-3-ylidene)acetate as a colourless viscous oil (815 mg, 79%). The reaction mixture was then filtered through a pad of silica (washing with 30% EtOAc:Petrol ether) the solvent removed under reduced pressure