7-ethenyl-4-azaspiro[2.4]heptan-5-one

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

Procedure: Osmium tetroxide (55 mg, 0.22 mmol) and sodium periodate (1.4 g, 6.6 mmol) were added in portions to a solution of 7-ethenyl-4-azaspiro[2.4]heptan-5-one (0.50 g, 3.3 mmol) in methanol (8 mL) and water (12 mL) at room temperature. The reaction mixture was stirred at room temperature for 4 hours. The reaction mixture was filtered and the filtrate was dried under reduced pressure to afford 5-oxo-4-azaspiro[2.4]heptane-7-carbaldehyde. The material was used in the next step without purification. MS ESI calc'd. for C7H10NO2 [M+H]+ 140. found 140. The reaction mixture was filtered the filtrate was dried under reduced pressure

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

Procedure: Osmium tetroxide (55 mg, 0.22 mmol) and sodium periodate (1.4 g, 6.6 mmol) were added in portions to a solution of 7-ethenyl-4-azaspiro[2.4]heptan-5-one (0.50 g, 3.3 mmol) in methanol (8 mL) and water (12 mL) at room temperature. The reaction mixture was stirred at room temperature for 4 hours. The reaction mixture was filtered and the filtrate was dried under reduced pressure to afford 5-oxo-4-azaspiro[2.4]heptane-7-carbaldehyde. The material was used in the next step without purification. MS ESI calc'd. for C7H10NO2 [M+H]+ 140. found 140. The reaction mixture was filtered the filtrate was dried under reduced pressure

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

Procedure: Ethyl magnesium bromide (3.0 M in ether, 2.2 mL, 6.6 mmol) was added dropwise over a period of 1 hour to a solution of ethyl 3-cyanopent-4-enoate (500 mg, 3.27 mmol) and Ti(Oi-Pr)4 (1.1 mL, 3.6 mmol) in diethylether (16.4 mL) at room temperature. The reaction mixture was diluted by the dropwise addition of water (3.27 mL) and stirred at room temperature for an additional 30 minutes. The reaction mixture was filtered and the filtrate was concentrated under reduced pressure to afford the crude product residue. The crude product residue was purified by silica gel chromatography (1:1 ethyl acetate/petroleum ether, Rf=0.3) to afford 7-ethenyl-4-azaspiro[2.4]heptan-5-one as a white solid. MS ESI calc'd. for C8H12NO [M+H]+ 138. found 138. 1H NMR (400 MHz, CDCl3) δ 6.09 (br s, 1H), 5.68-5.60 (m, 1H), 5.08-5.00 (m, 2H), 3.01-2.96 (m, 1H), 2.70-2.64 (m, 1H), 2.40-2.36 (m, 1H), 0.83-0.75 (m, 2H), 0.65-0.58 (m, 2H). The reaction mixture was filtered the filtrate was concentrated under reduced pressure to afford the crude product residue The crude product residue was purified by silica gel chromatography (1:1 ethyl acetate/petroleum ether, Rf=0.3)

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

Procedure: Osmium tetroxide (55 mg, 0.22 mmol) and sodium periodate (1.4 g, 6.6 mmol) were added in portions to a solution of 7-ethenyl-4-azaspiro[2.4]heptan-5-one (0.50 g, 3.3 mmol) in methanol (8 mL) and water (12 mL) at room temperature. The reaction mixture was stirred at room temperature for 4 hours. The reaction mixture was filtered and the filtrate was dried under reduced pressure to afford 5-oxo-4-azaspiro[2.4]heptane-7-carbaldehyde. The material was used in the next step without purification. MS ESI calc'd. for C7H10NO2 [M+H]+ 140. found 140. The reaction mixture was filtered the filtrate was dried under reduced pressure

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

Procedure: Ethyl magnesium bromide (3.0 M in ether, 2.2 mL, 6.6 mmol) was added dropwise over a period of 1 hour to a solution of ethyl 3-cyanopent-4-enoate (500 mg, 3.27 mmol) and Ti(Oi-Pr)4 (1.1 mL, 3.6 mmol) in diethylether (16.4 mL) at room temperature. The reaction mixture was diluted by the dropwise addition of water (3.27 mL) and stirred at room temperature for an additional 30 minutes. The reaction mixture was filtered and the filtrate was concentrated under reduced pressure to afford the crude product residue. The crude product residue was purified by silica gel chromatography (1:1 ethyl acetate/petroleum ether, Rf=0.3) to afford 7-ethenyl-4-azaspiro[2.4]heptan-5-one as a white solid. MS ESI calc'd. for C8H12NO [M+H]+ 138. found 138. 1H NMR (400 MHz, CDCl3) δ 6.09 (br s, 1H), 5.68-5.60 (m, 1H), 5.08-5.00 (m, 2H), 3.01-2.96 (m, 1H), 2.70-2.64 (m, 1H), 2.40-2.36 (m, 1H), 0.83-0.75 (m, 2H), 0.65-0.58 (m, 2H). The reaction mixture was filtered the filtrate was concentrated under reduced pressure to afford the crude product residue The crude product residue was purified by silica gel chromatography (1:1 ethyl acetate/petroleum ether, Rf=0.3)