4-bromo-5-fluoro-2-(2-trimethylsilylethynyl)aniline

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: CuI (0.932 g, 4.89 mmol) was added to a solution of 4-bromo-5-fluoro-2-[(trimethylsilyl)ethynyl]aniline (0.700 g, 2.45 mmol) in DMF (25 mL). The resulting suspension was heated at 100° C. for 1 h. The reaction mixture was partitioned between 10% aqueous Na2S2O3 and Et2O. The aqueous layer was extracted with Et2O. The combined organic layers were washed with 5 N aqueous NaOH and brine, dried (Na2SO4), filtered, and concentrated. The crude product was used in the next step without further purification. The reaction mixture was partitioned between 10% aqueous Na2S2O3 and Et2O The aqueous layer was extracted with Et2O The combined organic layers were washed with 5 N aqueous NaOH and brine dried (Na2SO4) filtered concentrated The crude product was used in the next step without further purification

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

Procedure: Triethylamine (44 mL) followed by trimethylsilylacetylene (0.737 mL, 5.32 mmol) were added dropwise to a suspension of 4-bromo-5-fluoro-2-iodoaniline (1.4 g, 4.43 mmol), Pd(PPh3)2Cl2 (0.156 g, 0.222 mmol), and CuI (0.042 g, 0.222 mmol) at 0° C. The reaction was warmed to ambient temperature and stirred for 2 h. The reaction was concentrated, diluted with Et2O, and filtered through Celite. The filtrate was washed with brine, dried (Na2SO4), filtered and concentrated. Chromatography over silica eluting with 2-8% EtOAc/hexanes afforded the desired product as a yellow oil. The reaction was concentrated diluted with Et2O filtered through Celite The filtrate was washed with brine dried (Na2SO4) filtered concentrated