2-bromocyclopent-2-en-1-one

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

Procedure: To a -78° C. solution of 4-bromothioanisole (35.1 g, 173 mmol) in THF (500 mL) was added nBuLi (1.6 M in hexanes, 107.5 mL, 172 mmol). The solution was stirred for 45 min, then a solution of 2-bromo-2-cyclopenten-1-one (25.4 g, 158 mmol) in THF (150 mL was added and the mixture was allowed to warm to 0° C. and was quenched with saturated aqueous NH4Cl. The majority of the solvent was removed in vacuo and the residue was suspended in water and extracted with two portions of EtOAc. The organic layers were washed with brine, dried over MgSO4, filtered and concentrated. This material was dissolved in DMF (300 mL), cooled to 0° C. and treated with PDC (72.4 g, 192 mmol). The resulting mixture was warmed to r.t. and stirred for 2 h, then poured into H2O (1.2 L) and extracted with two 500 mL portions of EtOAc. The organic layers were washed with brine, dried over MgSO4, filtered and concentrated to give the title compound as a light brown solid which was used directly in the next step. was quenched with saturated aqueous NH4Cl The majority of the solvent was removed in vacuo extracted with two portions of EtOAc The organic layers were washed with brine dried over MgSO4 filtered concentrated This material was dissolved in DMF (300 mL) cooled to 0° C. The resulting mixture was warmed to r.t. stirred for 2 h extracted with two 500 mL portions of EtOAc The organic layers were washed with brine dried over MgSO4 filtered concentrated

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

Procedure: To a -78° C. solution of 4-bromothioanisole (35.1 g, 173 mmol) in THF (500 mL) was added nBuLi (1.6M in hexanes, 107.5 mL, 172 mmol). The solution was stirred for 45 min, then a solution of 2-bromo-2-cyclopenten-1-one (25.4 g, 158 mmol) in THF (150 mL) was added and the mixture was allowed to warm to 0° C. and was quenched with saturated aqueous NH4Cl. The majority of the solvent was removed in vacuo and the residue was suspended in water and extracted with two portions of EtOAc. The organic layers were washed with brine, dried over MgSO4, filtered and concentrated. This material was dissolved in DMF (300 mL), cooled to 0° C. and treated with PDC (72.4 g, 192 mmol). The resulting mixture was warmed to r.t. and stirred for 2 h, then poured into H2O (1.2 L) and extracted with two 500 mL portions of EtOAc. The organic layers were washed with brine, dried over MgSO4, filtered and concentrated to give the title compound as a light brown solid which was used directly in the next step. was quenched with saturated aqueous NH4Cl The majority of the solvent was removed in vacuo extracted with two portions of EtOAc The organic layers were washed with brine dried over MgSO4 filtered concentrated This material was dissolved in DMF (300 mL) cooled to 0° C. The resulting mixture was warmed to r.t. stirred for 2 h extracted with two 500 mL portions of EtOAc The organic layers were washed with brine dried over MgSO4 filtered concentrated

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

Procedure: To a stirred solution of 2-bromocyclopent-2-enone (1.00 g, 6.21 mmol) in H2O (25 mL), tetrabutylammonium bromide (400 mg, 1.24 mmol) and benzyl amine (790 mg, 7.45 mmol) were added at room temperature. The reaction mixture was stirred for 24 hours and then extracted with EtOAc (100 mL). The organic layer was separated, washed with brine, and dried over anhydrous Na2SO4, filtered and concentrated in vacuo. Purification of the residue on a silica gel column with 0 to 30% EtOAc/Hexanes afforded 6-benzyl-6-azabicyclo[3.1.0]hexan-2-one. MS ESI calc'd. for C12H13NO [M+H]+ 188. found 188. extracted with EtOAc (100 mL) The organic layer was separated washed with brine dried over anhydrous Na2SO4 filtered concentrated in vacuo Purification of the residue on a silica gel column with 0 to 30% EtOAc/Hexanes

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

Procedure: To a stirred solution of 2-bromocyclopent-2-enone (1.00 g, 6.21 mmol) in H2O (25 mL), tetrabutylammonium bromide (400 mg, 1.24 mmol) and benzyl amine (790 mg, 7.45 mmol) were added at room temperature. The reaction mixture was stirred for 24 hours and then extracted with EtOAc (100 mL). The organic layer was separated, washed with brine, and dried over anhydrous Na2SO4, filtered and concentrated in vacuo. Purification of the residue on a silica gel column with 0 to 30% EtOAc/Hexanes afforded 6-benzyl-6-azabicyclo[3.1.0]hexan-2-one. MS ESI calc'd. for C12H13NO [M+H]+ 188. found 188. extracted with EtOAc (100 mL) The organic layer was separated washed with brine dried over anhydrous Na2SO4 filtered concentrated in vacuo Purification of the residue on a silica gel column with 0 to 30% EtOAc/Hexanes

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

Procedure: To a -78° C. solution of 4-bromothioanisole (35.1 g, 173 mmol) in THF (500 mL) was added nBuLi (1.6 M in hexanes, 107.5 mL, 172 mmol). The solution was stirred for 45 min, then a solution of 2-bromo-2-cyclopenten-1-one (25.4 g, 158 mmol) in THF (150 mL was added and the mixture was allowed to warm to 0° C. and was quenched with saturated aqueous NH4Cl. The majority of the solvent was removed in vacuo and the residue was suspended in water and extracted with two portions of EtOAc. The organic layers were washed with brine, dried over MgSO4, filtered and concentrated. This material was dissolved in DMF (300 mL), cooled to 0° C. and treated with PDC (72.4 g, 192 mmol). The resulting mixture was warmed to r.t. and stirred for 2 h, then poured into H2O (1.2 L) and extracted with two 500 mL portions of EtOAc. The organic layers were washed with brine, dried over MgSO4, filtered and concentrated to give the title compound as a light brown solid which was used directly in the next step. was quenched with saturated aqueous NH4Cl The majority of the solvent was removed in vacuo extracted with two portions of EtOAc The organic layers were washed with brine dried over MgSO4 filtered concentrated This material was dissolved in DMF (300 mL) cooled to 0° C. The resulting mixture was warmed to r.t. stirred for 2 h extracted with two 500 mL portions of EtOAc The organic layers were washed with brine dried over MgSO4 filtered concentrated

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

Procedure: To a -78° C. solution of 4-bromothioanisole (35.1 g, 173 mmol) in THF (500 mL) was added nBuLi (1.6M in hexanes, 107.5 mL, 172 mmol). The solution was stirred for 45 min, then a solution of 2-bromo-2-cyclopenten-1-one (25.4 g, 158 mmol) in THF (150 mL) was added and the mixture was allowed to warm to 0° C. and was quenched with saturated aqueous NH4Cl. The majority of the solvent was removed in vacuo and the residue was suspended in water and extracted with two portions of EtOAc. The organic layers were washed with brine, dried over MgSO4, faltered and concentrated. This material was dissolved in DMF (300 mL), cooled to 0° C. and treated with PDC (72.4 g, 192 mmol). The resulting mixture was warmed to r.t. and stirred for 2 h, then poured into H2O (1.2 L) and extracted with two 500 mL portions of EtOAc. The organic layers were washed with brine, dried over MgSO4, filtered and concentrated to give the title compound as a light brown solid which was used directly in the next step. was quenched with saturated aqueous NH4Cl The majority of the solvent was removed in vacuo extracted with two portions of EtOAc The organic layers were washed with brine dried over MgSO4 concentrated This material was dissolved in DMF (300 mL) cooled to 0° C. The resulting mixture was warmed to r.t. stirred for 2 h extracted with two 500 mL portions of EtOAc The organic layers were washed with brine dried over MgSO4 filtered concentrated

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

Procedure: To a -78° C. solution of 4-bromothioanisole (35.1 g, 173 mmol) in THF (500 mL) was added nBuLi (1.6M in hexanes, 107.5 mL, 172 mmol). The solution was stirred for 45 min, then a solution of 2-bromo-2-cyclopenten-1-one (25.4 g, 158 mmol) in THF (150 mL) was added and the mixture was allowed to warm to 0° C. and was quenched with saturated aqueous NH4Cl. The majority of the solvent was removed in vacuo and the residue was suspended in water and extracted with two portions of EtOAc. The organic layers were washed with brine, dried over MgSO4, filtered and concentrated. This material was dissolved in DMF (300 mL), cooled to 0° C. and treated with PDC (72.4 g, 192 mmol). The resulting mixture was warmed to r.t. and stirred for 2 h, then poured into H2O (1.2 L) and extracted with two 500 mL portions of EtOAc. The organic layers were washed with brine, dried over MgSO4, filtered and concentrated to give the title compound as a light brown solid which was used directly in the next step. was quenched with saturated aqueous NH4Cl The majority of the solvent was removed in vacuo extracted with two portions of EtOAc The organic layers were washed with brine dried over MgSO4 filtered concentrated This material was dissolved in DMF (300 mL) cooled to 0° C. The resulting mixture was warmed to r.t. stirred for 2 h extracted with two 500 mL portions of EtOAc The organic layers were washed with brine dried over MgSO4 filtered concentrated