4-fluoro-2-N-(4-fluorophenyl)benzene-1,2-diamine

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

Procedure: (5-Fluoro-2-nitrophenyl)-(4-fluorophenyl)amine (2.94 g, 11.76 mmol) was dissolved in EtOAc (120 mL) and the flask evacuated and flushed with nitrogen gas. 10% Pd/C (0.29 g) was added and the reaction mixture stirred at RT, under an atmosphere of hydrogen overnight. The resultant mixture was filtered through Celite® and the filtrate concentrated in vacuo to afford the title compound as an orange oil (2.67 g, 91%). 1H NMR (CDCl3, 400 MHz): δ 7.01-6.92 (2H, m), 6.87-6.68 (4H, m), 6.61 (1H, td, J=8.35, 2.79 Hz), 5.24 (1H, s), 3.46 (2H, s) the flask evacuated flushed with nitrogen gas 10% Pd/C (0.29 g) was added The resultant mixture was filtered through Celite® the filtrate concentrated in vacuo

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

Procedure: (5-Fluoro-2-nitrophenyl)-(4-fluorophenyl)amine (2.94 g, 11.76 mmol) was dissolved in EtOAc (120 mL) and the flask evacuated and flushed with nitrogen gas. 10% Pd/C (0.29 g) was added and the reaction mixture stirred at RT, under an atmosphere of hydrogen overnight. The resultant mixture was filtered through Celite® and the filtrate concentrated in vacuo to afford the title compound as an orange oil (2.67 g, 91%). 1H NMR (CDCl3, 400 MHz): δ 7.01-6.92 (2H, m), 6.87-6.68 (4H, m), 6.61 (1H, td, J=8.35, 2.79 Hz), 5.24 (1H, s), 3.46 (2H, s) the flask evacuated flushed with nitrogen gas 10% Pd/C (0.29 g) was added The resultant mixture was filtered through Celite® the filtrate concentrated in vacuo

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

Procedure: (5-Fluoro-2-nitrophenyl)-(4-fluorophenyl)amine (2.94 g, 11.76 mmol) was dissolved in EtOAc (120 mL) and the flask evacuated and flushed with nitrogen gas. 10% Pd/C (0.29 g) was added and the reaction mixture stirred at RT, under an atmosphere of hydrogen overnight. The resultant mixture was filtered through Celite® and the filtrate concentrated in vacuo to afford the title compound as an orange oil (2.67 g, 91%). 1H NMR (CDCl3, 400 MHz): δ 7.01-6.92 (2H, m), 6.87-6.68 (4H, m), 6.61 (1H, td, J=8.35, 2.79 Hz), 5.24 (1H, s), 3.46 (2H, s) the flask evacuated flushed with nitrogen gas 10% Pd/C (0.29 g) was added The resultant mixture was filtered through Celite® the filtrate concentrated in vacuo

Conditions: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a −10° C. solution (NaCl-ice bath) of Fmoc-L-Ala-OH (4.45 g, 14.30 mmol) and N-methylmorpholine (1.573 mL, 14.30 mmol) in DCM (34.1 mL) was added isobutyl chloroformate (1.782 mL, 13.62 mmol). The resulting cloudy colorless mixture was stirred at −10° C. for 30 min. To the mixture was then added a solution of 5-fluoro-N1-(4-fluorophenyl)benzene-1,2-diamine (1.500 g, 6.81 mmol) in DCM (12.75 mL). The resulting mixture was stirred at −10° C. for 1 h, to which the cold mixture was added satd. aq. NH4Cl solution (100 mL). The precipitate was collected by filtration and washed with water (100 mL) to give (S)-(9H-fluoren-9-yl)methyl 1-(4-fluoro-2-(4-fluorophenylamino)phenylamino)-1-oxopropan-2-ylcarbamate as an off-white solid: 1H NMR (400 MHz, DMSO-d6) δ ppm 9.42 (1H, s), 7.89 (2H, d, J=7.6 Hz), 7.63-7.78 (3H, m), 7.22-7.46 (6H, m), 6.96-7.14 (4H, m), 6.83 (1H, dd, J=11.2, 2.7 Hz), 6.67 (1H, td, J=8.5, 2.8 Hz), 4.11-4.33 (4H, m), 1.28 (3H, d, J=7.0 Hz); LC-MS (ESI) m/z 514.2 [M+H]+. The off-white solid was carried on crude without purification. The resulting mixture was stirred at −10° C. for 1 h, to which the cold mixture was added satd The precipitate was collected by filtration washed with water (100 mL)

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

Procedure: (5-Fluoro-2-nitrophenyl)-(4-fluorophenyl)amine (2.94 g, 11.76 mmol) was dissolved in EtOAc (120 mL) and the flask evacuated and flushed with nitrogen gas. 10% Pd/C (0.29 g) was added and the reaction mixture stirred at RT, under an atmosphere of hydrogen overnight. The resultant mixture was filtered through Celite® and the filtrate concentrated in vacuo to afford the title compound as an orange oil (2.67 g, 91%). 1H NMR (CDCl3, 400 MHz): δ 7.01-6.92 (2H, m), 6.87-6.68 (4H, m), 6.61 (1H, td, J=8.35, 2.79 Hz), 5.24 (1H, s), 3.46 (2H, s) the flask evacuated flushed with nitrogen gas 10% Pd/C (0.29 g) was added The resultant mixture was filtered through Celite® the filtrate concentrated in vacuo