tert-butyl (E)-hept-2-enoate

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

Procedure: 74.79 ml (312 mmol) of 1,2-(di-tert-butyl)trimethylamine were added to a stirred mixture of 5 g (39 mmol) of (E)-2-heptenoic acid in 100 ml of toluene at 80° C. The mixture was stirred under reflux for 30 minutes and then cooled to room temperature. The mixture was washed in sequence with water and saturated sodium bicarbonate solution, then dried over anhydrous magnesium sulphate and filtered. The solvent was removed by evaporation. There were obtained 7.5 g of tert-butyl (E)-2-heptenoate as a yellow oil; MS: m/e 185.0 [M+H]. under reflux for 30 minutes The mixture was washed in sequence with water and saturated sodium bicarbonate solution dried over anhydrous magnesium sulphate filtered The solvent was removed by evaporation

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

Procedure: 74.79 ml (312 mmol) of 1,2-(di-tert-butyl)trimethylamine were added to a stirred mixture of 5 g (39 mmol) of (E)-2-heptenoic acid in 100 ml of toluene at 80° C. The mixture was stirred under reflux for 30 minutes and then cooled to room temperature. The mixture was washed in sequence with water and saturated sodium bicarbonate solution, then dried over anhydrous magnesium sulphate and filtered. The solvent was removed by evaporation. There were obtained 7.5 g of tert-butyl (E)-2-heptenoate as a yellow oil; MS: m/e 185.0 [M+H]. under reflux for 30 minutes The mixture was washed in sequence with water and saturated sodium bicarbonate solution dried over anhydrous magnesium sulphate filtered The solvent was removed by evaporation

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

Procedure: A solution of 0.66 ml of (S)-(−)-N-benzyl-α-methylbenzylamine in 10 ml of tetrahydrofuran was cooled to 0° C. and 1.88 ml of a 1.6M solution of n-butyllithium in hexane were added dropwise via a syringe. The resulting dark pink solution was stirred at 0° C. for 45 minutes and then cooled to −78° C. A solution of 0.184 g of tert-butyl (E)-2-heptenoate in 2 ml of anhydrous diethyl ether was added and the mixture was stirred for 2 hours at −78° C. 0.37 g of solid (1S)-(+)-(10-camphorsulphonyl)oxaziridine was added and the mixture was stirred at −78° C. for 1 hour. The mixture was warmed to 0° C. and a saturated ammonium chloride solution was added. The tetrahydrofuran was evaporated and the aqueous phase was diluted with water and extracted with dichloromethane. The organic phase was dried over magnesium sulphate, evaporated and purified by chromatography on silica gel using a 10% solution of diethyl ether in hexane for the elution to give 0.35 g of tert-butyl 3(S)-[N-benzyl-N-(α(S)-methylbenzyl)amino]-2(S)-hydroxyheptanoate as a colorless oil, MS: m/e 412.2 [M+H]+. cooled to −78° C the mixture was stirred for 2 hours at −78° C the mixture was stirred at −78° C. for 1 hour The mixture was warmed to 0° C. The tetrahydrofuran was evaporated the aqueous phase was diluted with water extracted with dichloromethane The organic phase was dried over magnesium sulphate evaporated purified by chromatography on silica gel using a 10% solution of diethyl ether in hexane for the elution

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

Procedure: n-Butyllithium (2.5M in hexanes, 27.66 ml) was added to a stirred solution of (S)—N-benzyl-1-phenylethanamine (15.59 g) in THF (150 mL) at −78° C. The reaction mixture was stirred for 30 mins then the product from step (i) (8.5 g) in THF (50 mL) was added and the reaction mixture stirred for 2 h at −78° C. The mixture was quenched with sat. NH4Cl solution and warmed to rt. The product was partitioned between EtOAc and water, the organic phase was washed with water, dried, and evaporated. The residue was purified by column chromatography eluting with 5% EtOAc in isohexane to give the subtitle compound 12.7 g. the reaction mixture stirred for 2 h at −78° C The mixture was quenched with sat. NH4Cl solution The product was partitioned between EtOAc and water the organic phase was washed with water dried evaporated The residue was purified by column chromatography eluting with 5% EtOAc in isohexane

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

Procedure: n-Butyllithium (2.5M in hexanes, 27.66 ml) was added to a stirred solution of (S)—N-benzyl-1-phenylethanamine (15.59 g) in THF (150 mL) at −78° C. The reaction mixture was stirred for 30 mins then the product from step (i) (8.5 g) in THF (50 mL) was added and the reaction mixture stirred for 2 h at −78° C. The mixture was quenched with sat. NH4Cl solution and warmed to rt. The product was partitioned between EtOAc and water, the organic phase was washed with water, dried, and evaporated. The residue was purified by column chromatography eluting with 5% EtOAc in isohexane to give the subtitle compound 12.7 g. the reaction mixture stirred for 2 h at −78° C The mixture was quenched with sat. NH4Cl solution The product was partitioned between EtOAc and water the organic phase was washed with water dried evaporated The residue was purified by column chromatography eluting with 5% EtOAc in isohexane

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

Procedure: To a solution of valeraldehyde (5.81 g) in THF (100 mL) was added tert-butoxycarbonylmethylenetriphenylphosphorane (25.4 g) and the reaction mixture stirred for 16 h at rt. The solvents were evaporated, the residue slurried in diethyl ether and filtered. The filtrate was evaporated and the residue purified by chromatography eluting with 3% EtOAc in isohexane to give the subtitle compound 8.5 g. The solvents were evaporated filtered The filtrate was evaporated the residue purified by chromatography eluting with 3% EtOAc in isohexane

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

Procedure: To a solution of valeraldehyde (5.81 g) in THF (100 mL) was added tert-butoxycarbonylmethylenetriphenylphosphorane (25.4 g) and the reaction mixture stirred for 16 h at rt. The solvents were evaporated, the residue slurried in diethyl ether and filtered. The filtrate was evaporated and the residue purified by chromatography eluting with 3% EtOAc in isohexane to give the subtitle compound 8.5 g. The solvents were evaporated filtered The filtrate was evaporated the residue purified by chromatography eluting with 3% EtOAc in isohexane

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

Procedure: To a solution of valeraldehyde (5.81 g) in THF (100 mL) was added tert-butoxycarbonylmethylenetriphenylphosphorane (25.4 g) and the reaction mixture stirred for 16 h at rt. The solvents were evaporated, the residue slurried in diethyl ether and filtered. The filtrate was evaporated and the residue purified by chromatography eluting with 3% EtOAc in isohexane to give the subtitle compound 8.5 g. The solvents were evaporated filtered The filtrate was evaporated the residue purified by chromatography eluting with 3% EtOAc in isohexane

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

Procedure: 74.79 ml (312 mmol) of 1,2-(di-tert-butyl)trimethylamine were added to a stirred mixture of 5 g (39 mmol) of (E)-2-heptenoic acid in 100 ml of toluene at 80° C. The mixture was stirred under reflux for 30 minutes and then cooled to room temperature. The mixture was washed in sequence with water and saturated sodium bicarbonate solution, then dried over anhydrous magnesium sulphate and filtered. The solvent was removed by evaporation. There were obtained 7.5 g of tert-butyl (E)-2-heptenoate as a yellow oil; MS: m/e 185.0 [M+H]. under reflux for 30 minutes The mixture was washed in sequence with water and saturated sodium bicarbonate solution dried over anhydrous magnesium sulphate filtered The solvent was removed by evaporation

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

Procedure: A solution of 0.66 ml of (S)-(−)-N-benzyl-α-methylbenzylamine in 10 ml of tetrahydrofuran was cooled to 0° C. and 1.88 ml of a 1.6M solution of n-butyllithium in hexane were added dropwise via a syringe. The resulting dark pink solution was stirred at 0° C. for 45 minutes and then cooled to −78° C. A solution of 0.184 g of tert-butyl (E)-2-heptenoate in 2 ml of anhydrous diethyl ether was added and the mixture was stirred for 2 hours at −78° C. 0.37 g of solid (1S)-(+)-(10-camphorsulphonyl)oxaziridine was added and the mixture was stirred at −78° C. for 1 hour. The mixture was warmed to 0° C. and a saturated ammonium chloride solution was added. The tetrahydrofuran was evaporated and the aqueous phase was diluted with water and extracted with dichloromethane. The organic phase was dried over magnesium sulphate, evaporated and purified by chromatography on silica gel using a 10% solution of diethyl ether in hexane for the elution to give 0.35 g of tert-butyl 3(S)-[N-benzyl-N-(α(S)-methylbenzyl)amino]-2(S)-hydroxyheptanoate as a colorless oil, MS: m/e 412.2 [M+H]+. cooled to −78° C the mixture was stirred for 2 hours at −78° C the mixture was stirred at −78° C. for 1 hour The mixture was warmed to 0° C. The tetrahydrofuran was evaporated the aqueous phase was diluted with water extracted with dichloromethane The organic phase was dried over magnesium sulphate evaporated purified by chromatography on silica gel using a 10% solution of diethyl ether in hexane for the elution