3-methyl-2-N-phenylbenzene-1,2-diamine

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

Procedure: To a solution of 3-methyl-N2-phenyl-benzene-1,2-diamine (852 mg, 4.3 mmol) in anhydrous DCM (20 mL) were added (S)-2-benzyloxycarbonylaminopropionic acid (1.44 g, 6.45 mmol), HOBt (639 mg, 4.73 mmol), 4-methylmorpholine (1.04 mL, 9.46 mmol) and N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (1.24 g, 6.45 mmol). The mixture was stirred at RT for 6.5 h and then partitioned between DCM (100 mL) and water. The organic layer was then washed with brine, dried (Na2SO4) and concentrated in vacuo. The resulting residue was dissolved in AcOH (10 mL) and heated to 65° C. for 18 h. After cooling to RT, volatiles were removed under reduced pressure and the residue diluted with EtOAc (100 mL). The organic layer was washed with a saturated solution of NaHCO3, followed by brine, then dried (Na2SO4) and concentrated in vacuo affording [(S)-1-(7-Methyl-1-phenyl-1H-benzoimidazol-2-yl)ethyl]carbamic acid benzyl ester as brown foam (1.5 g, 90%). LCMS: RT 3.07 min [M+H]+ 386.2. partitioned between DCM (100 mL) and water The organic layer was then washed with brine dried (Na2SO4) concentrated in vacuo The resulting residue was dissolved in AcOH (10 mL) heated to 65° C. for 18 h After cooling to RT volatiles were removed under reduced pressure the residue diluted with EtOAc (100 mL) The organic layer was washed with a saturated solution of NaHCO3 dried (Na2SO4) concentrated in vacuo

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

Procedure: To a solution of 3-methyl-N2-phenyl-benzene-1,2-diamine (852 mg, 4.3 mmol) in anhydrous DCM (20 mL) were added (S)-2-benzyloxycarbonylaminopropionic acid (1.44 g, 6.45 mmol), HOBt (639 mg, 4.73 mmol), 4-methylmorpholine (1.04 mL, 9.46 mmol) and N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (1.24 g, 6.45 mmol). The mixture was stirred at RT for 6.5 h and then partitioned between DCM (100 mL) and water. The organic layer was then washed with brine, dried (Na2SO4) and concentrated in vacuo. The resulting residue was dissolved in AcOH (10 mL) and heated to 65° C. for 18 h. After cooling to RT, volatiles were removed under reduced pressure and the residue diluted with EtOAc (100 mL). The organic layer was washed with a saturated solution of NaHCO3, followed by brine, then dried (Na2SO4) and concentrated in vacuo affording [(S)-1-(7-Methyl-1-phenyl-1H-benzoimidazol-2-yl)ethyl]carbamic acid benzyl ester as brown foam (1.5 g, 90%). LCMS: RT 3.07 min [M+H]+ 386.2. partitioned between DCM (100 mL) and water The organic layer was then washed with brine dried (Na2SO4) concentrated in vacuo The resulting residue was dissolved in AcOH (10 mL) heated to 65° C. for 18 h After cooling to RT volatiles were removed under reduced pressure the residue diluted with EtOAc (100 mL) The organic layer was washed with a saturated solution of NaHCO3 dried (Na2SO4) concentrated in vacuo

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

Procedure: A mixture of (2-methyl-6-nitrophenyl)phenylamine (981 mg, 4.3 mmol) and 10% Pd/C (981 mg) in EtOAc (20 mL) was degassed with a stream of nitrogen and then stirred at RT under a hydrogen atmosphere for 4 h. The suspension was then filtered through a PTFE frit and the filtrate was concentrated in vacuo affording 3-Methyl-N2-phenylbenzene-1,2-diamine as a yellow solid (852 mg, 100%). LCMS: RT 3.02 min [M+H]+ 199.0 was degassed with a stream of nitrogen The suspension was then filtered through a PTFE frit the filtrate was concentrated in vacuo

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

Procedure: A mixture of (2-methyl-6-nitrophenyl)phenylamine (981 mg, 4.3 mmol) and 10% Pd/C (981 mg) in EtOAc (20 mL) was degassed with a stream of nitrogen and then stirred at RT under a hydrogen atmosphere for 4 h. The suspension was then filtered through a PTFE frit and the filtrate was concentrated in vacuo affording 3-Methyl-N2-phenylbenzene-1,2-diamine as a yellow solid (852 mg, 100%). LCMS: RT 3.02 min [M+H]+ 199.0 was degassed with a stream of nitrogen The suspension was then filtered through a PTFE frit the filtrate was concentrated in vacuo

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

Procedure: To a solution of 3-methyl-N2-phenyl-benzene-1,2-diamine (852 mg, 4.3 mmol) in anhydrous DCM (20 mL) were added (S)-2-benzyloxycarbonylaminopropionic acid (1.44 g, 6.45 mmol), HOBt (639 mg, 4.73 mmol), 4-methylmorpholine (1.04 mL, 9.46 mmol) and N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (1.24 g, 6.45 mmol). The mixture was stirred at RT for 6.5 h and then partitioned between DCM (100 mL) and water. The organic layer was then washed with brine, dried (Na2SO4) and concentrated in vacuo. The resulting residue was dissolved in AcOH (10 mL) and heated to 65° C. for 18 h. After cooling to RT, volatiles were removed under reduced pressure and the residue diluted with EtOAc (100 mL). The organic layer was washed with a saturated solution of NaHCO3, followed by brine, then dried (Na2SO4) and concentrated in vacuo affording [(S)-1-(7-Methyl-1-phenyl-1H-benzoimidazol-2-yl)ethyl]carbamic acid benzyl ester as brown foam (1.5 g, 90%). LCMS: RT 3.07 min [M+H]+ 386.2. partitioned between DCM (100 mL) and water The organic layer was then washed with brine dried (Na2SO4) concentrated in vacuo The resulting residue was dissolved in AcOH (10 mL) heated to 65° C. for 18 h After cooling to RT volatiles were removed under reduced pressure the residue diluted with EtOAc (100 mL) The organic layer was washed with a saturated solution of NaHCO3 dried (Na2SO4) concentrated in vacuo

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

Procedure: A mixture of (2-methyl-6-nitrophenyl)phenylamine (981 mg, 4.3 mmol) and 10% Pd/C (981 mg) in EtOAc (20 mL) was degassed with a stream of nitrogen and then stirred at RT under a hydrogen atmosphere for 4 h. The suspension was then filtered through a PTFE frit and the filtrate was concentrated in vacuo affording 3-Methyl-N2-phenylbenzene-1,2-diamine as a yellow solid (852 mg, 100%). LCMS: RT 3.02 min [M+H]+ 199.0 was degassed with a stream of nitrogen The suspension was then filtered through a PTFE frit the filtrate was concentrated in vacuo

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

Procedure: To a solution of 3-methyl-N2-phenyl-benzene-1,2-diamine (852 mg, 4.3 mmol) in anhydrous DCM (20 mL) were added (S)-2-benzyloxycarbonylaminopropionic acid (1.44 g, 6.45 mmol), HOBt (639 mg, 4.73 mmol), 4-methylmorpholine (1.04 mL, 9.46 mmol) and N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (1.24 g, 6.45 mmol). The mixture was stirred at RT for 6.5 h and then partitioned between DCM (100 mL) and water. The organic layer was then washed with brine, dried (Na2SO4) and concentrated in vacuo. The resulting residue was dissolved in AcOH (10 mL) and heated to 65° C. for 18 h. After cooling to RT, volatiles were removed under reduced pressure and the residue diluted with EtOAc (100 mL). The organic layer was washed with a saturated solution of NaHCO3, followed by brine, then dried (Na2SO4) and concentrated in vacuo affording [(S)-1-(7-Methyl-1-phenyl-1H-benzoimidazol-2-yl)ethyl]carbamic acid benzyl ester as brown foam (1.5 g, 90%). LCMS: RT 3.07 min [M+H]+ 386.2. partitioned between DCM (100 mL) and water The organic layer was then washed with brine dried (Na2SO4) concentrated in vacuo The resulting residue was dissolved in AcOH (10 mL) heated to 65° C. for 18 h After cooling to RT volatiles were removed under reduced pressure the residue diluted with EtOAc (100 mL) The organic layer was washed with a saturated solution of NaHCO3 dried (Na2SO4) concentrated in vacuo

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

Procedure: A mixture of (2-methyl-6-nitrophenyl)phenylamine (981 mg, 4.3 mmol) and 10% Pd/C (981 mg) in EtOAc (20 mL) was degassed with a stream of nitrogen and then stirred at RT under a hydrogen atmosphere for 4 h. The suspension was then filtered through a PTFE frit and the filtrate was concentrated in vacuo affording 3-Methyl-N2-phenylbenzene-1,2-diamine as a yellow solid (852 mg, 100%). LCMS: RT 3.02 min [M+H]+ 199.0 was degassed with a stream of nitrogen The suspension was then filtered through a PTFE frit the filtrate was concentrated in vacuo