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

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

Procedure: To a stirred solution of ethyl (2E)-3-cyclopropylacrylate (5.3 g, 37.9 mmol) and TFA (0.43 g, 3.79 mmol) in DCM (100 mL) was added dropwise {benzyl[(trimethylsilyl)methyl]amino}methanol (13.5 g, 56.8 mmol) at 0° C. After the addition, the mixture was refluxed overnight. TLC (petroleum ether: EtOAc 10:1) indicated most of ethyl (2E)-3-cyclopropylacrylate was consumed. The reaction mixture was quenched with sat. NaHCO3 (100 mL), brine (100 mL), dried over Na2SO4 and concentrated in vacuo. The residue was purified by column chromatography (silica gel, petroleum ether: EtOAc=50:1 to 30:1) to give the title compound (5.8 g, 54% yield) as a yellow oil. After the addition the mixture was refluxed overnight was consumed The reaction mixture was quenched with sat. NaHCO3 (100 mL), brine (100 mL) dried over Na2SO4 concentrated in vacuo The residue was purified by column chromatography (silica gel, petroleum ether: EtOAc=50:1 to 30:1)

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

Procedure: To a stirred suspension of NaH (60% in oil, 2.1 g, 51.5 mmol) in dry THF (50 mL) was added dropwise ethyl(diethoxyphosphoryl)acetate (10.6 g, 47.1 mmol) at 0° C. under N2 atmosphere. The resulting mixture was stirred at 0° C. for 0.5 hr and added dropwise a solution of cyclopropanecarbaldehyde (3.0 g, 42.9 mmol) in dry THF (50 mL). After the addition, the mixture was stirred at rt for 16 hrs. Then the reaction mixture was quenched by addition of 5% NH4Cl (100 mL) at 0° C. and extracted with EtOAc (100 mL). The organic layer was washed with brine (100 mL), dried over Na2SO4 and concentrated in vacuo. The residue was purified by column chromatography (silica gel, petroleum ether: EtOAc=30:1) to give the title compound (5.3 g, 88.3% yield) as a colorless oil. After the addition the mixture was stirred at rt for 16 hrs Then the reaction mixture was quenched by addition of 5% NH4Cl (100 mL) at 0° C. extracted with EtOAc (100 mL) The organic layer was washed with brine (100 mL) dried over Na2SO4 concentrated in vacuo The residue was purified by column chromatography (silica gel, petroleum ether: EtOAc=30:1)

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

Procedure: To a stirred suspension of NaH (60% in oil, 2.1 g, 51.5 mmol) in dry THF (50 mL) was added dropwise ethyl(diethoxyphosphoryl)acetate (10.6 g, 47.1 mmol) at 0° C. under N2 atmosphere. The resulting mixture was stirred at 0° C. for 0.5 hr and added dropwise a solution of cyclopropanecarbaldehyde (3.0 g, 42.9 mmol) in dry THF (50 mL). After the addition, the mixture was stirred at rt for 16 hrs. Then the reaction mixture was quenched by addition of 5% NH4Cl (100 mL) at 0° C. and extracted with EtOAc (100 mL). The organic layer was washed with brine (100 mL), dried over Na2SO4 and concentrated in vacuo. The residue was purified by column chromatography (silica gel, petroleum ether: EtOAc=30:1) to give the title compound (5.3 g, 88.3% yield) as a colorless oil. After the addition the mixture was stirred at rt for 16 hrs Then the reaction mixture was quenched by addition of 5% NH4Cl (100 mL) at 0° C. extracted with EtOAc (100 mL) The organic layer was washed with brine (100 mL) dried over Na2SO4 concentrated in vacuo The residue was purified by column chromatography (silica gel, petroleum ether: EtOAc=30:1)

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

Procedure: To a stirred solution of ethyl (2E)-3-cyclopropylacrylate (5.3 g, 37.9 mmol) and TFA (0.43 g, 3.79 mmol) in DCM (100 mL) was added dropwise {benzyl[(trimethylsilyl)methyl]amino}methanol (13.5 g, 56.8 mmol) at 0° C. After the addition, the mixture was refluxed overnight. TLC (petroleum ether: EtOAc 10:1) indicated most of ethyl (2E)-3-cyclopropylacrylate was consumed. The reaction mixture was quenched with sat. NaHCO3 (100 mL), brine (100 mL), dried over Na2SO4 and concentrated in vacuo. The residue was purified by column chromatography (silica gel, petroleum ether: EtOAc=50:1 to 30:1) to give the title compound (5.8 g, 54% yield) as a yellow oil. After the addition the mixture was refluxed overnight was consumed The reaction mixture was quenched with sat. NaHCO3 (100 mL), brine (100 mL) dried over Na2SO4 concentrated in vacuo The residue was purified by column chromatography (silica gel, petroleum ether: EtOAc=50:1 to 30:1)

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

Procedure: To a stirred suspension of NaH (60% in oil, 2.1 g, 51.5 mmol) in dry THF (50 mL) was added dropwise ethyl(diethoxyphosphoryl)acetate (10.6 g, 47.1 mmol) at 0° C. under N2 atmosphere. The resulting mixture was stirred at 0° C. for 0.5 hr and added dropwise a solution of cyclopropanecarbaldehyde (3.0 g, 42.9 mmol) in dry THF (50 mL). After the addition, the mixture was stirred at rt for 16 hrs. Then the reaction mixture was quenched by addition of 5% NH4Cl (100 mL) at 0° C. and extracted with EtOAc (100 mL). The organic layer was washed with brine (100 mL), dried over Na2SO4 and concentrated in vacuo. The residue was purified by column chromatography (silica gel, petroleum ether: EtOAc=30:1) to give the title compound (5.3 g, 88.3% yield) as a colorless oil. After the addition the mixture was stirred at rt for 16 hrs Then the reaction mixture was quenched by addition of 5% NH4Cl (100 mL) at 0° C. extracted with EtOAc (100 mL) The organic layer was washed with brine (100 mL) dried over Na2SO4 concentrated in vacuo The residue was purified by column chromatography (silica gel, petroleum ether: EtOAc=30:1)