苄基 2,3,4,7-四氢氮杂-1-羧酸乙酯

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 2,3,4,7-tetrahydro-azepine-1-carboxylic acid benzyl ester (4.5 g, 19.45 mmol) in dichloromethane (50 mL) was added m-chloroperbenzoic acid (60 mmol). The mixture was stirred at ambient temperature for 16 hours. Saturated aqueous K2CO3 solution was added and the mixture was extracted with dichloromethane. The combined organic layers were washed with saturated aqueous NaHCO3 and brine, dried with MgSO4 and evaporated under vacuum. The crude epoxide was dissolved in an 8:1 methanol/water mixture (100 mL). Ammonium chloride (3.2 g, 60 mmol) and sodium azide (3.9 g, 60 mmol) were added and the mixture was heated at 60° C. for 48 hours. Most of the solvent was removed under vacuum. The residue was extracted with ethyl acetate. The combined organic layers were washed with saturated aqueous NaHCO3 (200 mL) and brine (200 mL), dried with MgSO4 and evaporated under vacuum. Flash chromatography of the residue (hexane/ethyl acetate 3:1) gave 4-azido-3-hydroxy-azepane-1-carboxylic acid benzyl ester (3.3 g). the mixture was extracted with dichloromethane The combined organic layers were washed with saturated aqueous NaHCO3 and brine dried with MgSO4 evaporated under vacuum The crude epoxide was dissolved in an 8:1 methanol/water mixture (100 mL) the mixture was heated at 60° C. for 48 hours Most of the solvent was removed under vacuum The residue was extracted with ethyl acetate The combined organic layers were washed with saturated aqueous NaHCO3 (200 mL) and brine (200 mL) dried with MgSO4 evaporated under vacuum

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 2,3,4,7-tetrahydro-azepine-1-carboxylic acid benzyl ester (4.5 g, 19.45 mmol) in dichloromethane (50 mL) was added m-chloroperbenzoic acid (60 mmol). The mixture was stirred at ambient temperature for 16 hours. Saturated aqueous K2CO3 solution was added and the mixture was extracted with dichloromethane. The combined organic layers were washed with saturated aqueous NaHCO3 and brine, dried with MgSO4 and evaporated under vacuum. The crude epoxide was dissolved in an 8:1 methanol/water mixture (100 mL). Ammonium chloride (3.2 g, 60 mmol) and sodium azide (3.9 g, 60 mmol) were added and the mixture was heated at 60° C. for 48 hours. Most of the solvent was removed under vacuum. The residue was extracted with ethyl acetate. The combined organic layers were washed with saturated aqueous NaHCO3 (200 mL) and brine (200 mL), dried with MgSO4 and evaporated under vacuum. Flash chromatography of the residue (hexane/ethyl acetate 3:1) gave 4-azido-3-hydroxy-azepane-1-carboxylic acid benzyl ester (3.3 g). the mixture was extracted with dichloromethane The combined organic layers were washed with saturated aqueous NaHCO3 and brine dried with MgSO4 evaporated under vacuum The crude epoxide was dissolved in an 8:1 methanol/water mixture (100 mL) the mixture was heated at 60° C. for 48 hours Most of the solvent was removed under vacuum The residue was extracted with ethyl acetate The combined organic layers were washed with saturated aqueous NaHCO3 (200 mL) and brine (200 mL) dried with MgSO4 evaporated under vacuum

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Allyl-pent-4-enyl-carbamic acid benzyl ester (15.5 g, 59.8 mmol) was dissolved in dichloromethane and bis(tricyclohexylphosphine)benzylidene ruthenium(IV) dichloride (1 g) was added. The mixture was refluxed under a nitrogen atmosphere until TLC analysis showed complete reaction. The solvent was evaporated under vacuum and the residue was purified by flash chromatography (ethyl acetate/hexane 1:9) to give 2,3,4,7-Tetrahydro-azepine-1-carboxylic acid benzyl ester (7.8 g). The mixture was refluxed under a nitrogen atmosphere until TLC analysis reaction The solvent was evaporated under vacuum the residue was purified by flash chromatography (ethyl acetate/hexane 1:9)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 2,3,4,7-tetrahydro-azepine-1-carboxylic acid benzyl ester (4.5 g, 19.45 mmol) in dichloromethyl (50 mL) was added m-chloroperbenzoic acid (60 mmol). The mixture was stirred at ambient temperature for 16 hours. Saturated aqueous K2CO3 solution was added and the mixture was extracted with dichloromethyl. The combined organic layers were washed with saturated aqueous NaHCO3 and brine, dried with MgSO4 and evaporated under vacuum. The crude epoxide was dissolved in a 8:1 methanol/water mixture (100 mL). Ammonium chloride (3.2 g, 60 mmol) and sodium azide (3.9 g, 60 mmol) was added and the mixture was heated at 60° C. for 48 hours. Most of the solvent was removed under vacuum. The residue was extracted with ethyl acetate. The combined organic layers were washed with saturated aqueous NaHCO3 (200 mL) and brine (200 mL), dried with MgSO4 and evaporated under vacuum. Flash chromatography of the residue (hexane/ethyl acetate 3:1) gave 3.3 g of 4-azido-3-hydroxy-azepane-1-carboxylic acid benzyl ester. the mixture was extracted with dichloromethyl The combined organic layers were washed with saturated aqueous NaHCO3 and brine dried with MgSO4 evaporated under vacuum The crude epoxide was dissolved in a 8:1 methanol/water mixture (100 mL) the mixture was heated at 60° C. for 48 hours Most of the solvent was removed under vacuum The residue was extracted with ethyl acetate The combined organic layers were washed with saturated aqueous NaHCO3 (200 mL) and brine (200 mL) dried with MgSO4 evaporated under vacuum

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 2,3,4,7-tetrahydro-azepine-1-carboxylic acid benzyl ester (4.5 g, 19.45 mmol) in dichloromethane (50 mL) was added m-chloroperbenzoic acid (60 mmol). The mixture was stirred at ambient temperature for 16 hours. Saturated aqueous K2CO3 solution was added and the mixture was extracted with dichloromethane. The combined organic layers were washed with saturated aqueous NaHCO3 and brine, dried with MgSO4 and evaporated under vacuum. The crude epoxide was dissolved in an 8:1 methanol/water mixture (100 mL). Ammonium chloride (3.2 g, 60 mmol) and sodium azide (3.9 g, 60 mmol) were added and the mixture was heated at 60° C. for 48 hours. Most of the solvent was removed under vacuum. The residue was extracted with ethyl acetate. The combined organic layers were washed with saturated aqueous NaHCO3 (200 mL) and brine (200 mL), dried with MgSO4 and evaporated under vacuum. Flash chromatography of the residue (hexane/ethyl acetate 3:1) gave 4-azido-3-hydroxy-azepane-1-carboxylic acid benzyl ester (3.3 g). the mixture was extracted with dichloromethane The combined organic layers were washed with saturated aqueous NaHCO3 and brine dried with MgSO4 evaporated under vacuum The crude epoxide was dissolved in an 8:1 methanol/water mixture (100 mL) the mixture was heated at 60° C. for 48 hours Most of the solvent was removed under vacuum The residue was extracted with ethyl acetate The combined organic layers were washed with saturated aqueous NaHCO3 (200 mL) and brine (200 mL) dried with MgSO4 evaporated under vacuum

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Allyl-pent-4-enyl-carbamic acid benzyl ester (15.5 g, 59.8 mmol) was dissolved in dichloromethane and bis(tricyclohexylphosphine)benzylidene ruthenium(IV) dichloride (1 g) was added. The mixture was refluxed under a nitrogen atmosphere until TLC analysis showed complete reaction. The solvent was evaporated under vacuum and the residue was purified by flash chromatography (ethyl acetate/hexane 1:9) to give 2,3,4,7-Tetrahydro-azepine-1-carboxylic acid benzyl ester (7.8 g). The mixture was refluxed under a nitrogen atmosphere until TLC analysis reaction The solvent was evaporated under vacuum the residue was purified by flash chromatography (ethyl acetate/hexane 1:9)