2-Phenylpent-4-enenitrile

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: 4-Cyano-4-phenyl-1-butene (15 g) is dissolved in 50 ml of ethanol and 3 drops of water whereupon 20 ml of sulfuric acid is added dropwise. The resulting mixture is warmed slowly and then heated under reflux for 6 hours. The reaction mixture is then poured into 100 ml of ice-cold water and extracted with 100 ml of benzene. The extract is dried over magnesium sulfate, and the solvent is distilled off under reduced pressure. The residue is distilled to give 7.0 g of ethyl 2-phenyl-4-pentenoate, boiling at 133°-137° C. (20 mmHg). The resulting mixture is warmed slowly heated under reflux for 6 hours extracted with 100 ml of benzene The extract is dried over magnesium sulfate the solvent is distilled off under reduced pressure The residue is distilled

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a cooled solution (−78° C.) of 4-cyano-4-phenyl-1-butene (6.23 g, 39.6 mmol) in anhydrous THF was added LIDS (1M in THF, 43.5 mL, 43.5 mmol) dropwise. The solution was stirred at −78° C. for 0.5 hour, then methyl bromoacetate (6.67 g, 43.6 mmol) was added dropwise. After stirring at room temperature for 24 hours, the reaction mixture was concentrated under vacuum. The residual material was purified using silica gel column chromatography eluting with 0-20% EtOAc in hexanes. The appropriate fractions were combined and concentrated to afford the title compound. 1H NMR (400 MHz, DMSO-d6) δ 7.38 (m, 5H), 5.57 (m, 1H), 5.14 (m, 2H), 3.49 (s, 3H), 3.49 (m, 2H), 2.78 (m, 2H) ppm. ES MS M+1=230. After stirring at room temperature for 24 hours the reaction mixture was concentrated under vacuum The residual material was purified eluting with 0-20% EtOAc in hexanes concentrated

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

Procedure: To a cooled solution (−78° C.) of benzyl cyanide (5.00 g, 42.7 mmol) in anhydrous THF was added LiHMDS (1M in THF, 46.9 mL, 46.9 mmol) dropwise. After 0.5 hour, allyl bromide (5.16 g, 42.6 mmol) was added dropwise to the reaction mixture. The reaction mixture was warmed to room temperature, and the solvent was removed under vacuum. The residual material was purified using silica gel column chromatography eluting with 100% hexanes. The appropriate fractions were combined and concentrated to afford the title compound. 1H NMR (400 MHz, DMSO-d6) δ 7.44 (m, 5H), 5.81 (m, 1H), 5.12 (m, 2H), 4.35 (t, J=6.9 Hz, 1H), 2.61 (m, 2H) ppm. ES MS M+1=158. the solvent was removed under vacuum The residual material was purified eluting with 100% hexanes concentrated