4-Benzyloxy-3,5-difluorophenylboronic acid

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

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

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

Procedure: To a solution of 4-bromo-1H-indazole-6-carbonitrile (1.0 g, 4.50 mmol) in dichloromethane (50 mL) was added {3,5-difluoro-4-[(phenylmethyl)oxy]phenyl}boronic acid {DE 4236105} (1.8 g, 6.82 mmol), pyridine (0.73 mL, 9.04 mmol), copper acetate (1.22 g, 6.74 mmol) and powdered 4A molecular sieves (5 g). The reaction mixture was stirred at room temperature in the presence of air for 6 days. Celite was added to the mixture and stirred for 5 mins then the mixture was filtered through a pad of celite and then the filtrate was washed with water, dried over magnesium sulphate, filtered and concentrated. The product was purified by silica gel chromatography eluting with 10-100% ethyl acetate in hexane to yield the title compound (D36) (944 mg). Celite was added to the mixture stirred for 5 mins the mixture was filtered through a pad of celite the filtrate was washed with water dried over magnesium sulphate filtered concentrated The product was purified by silica gel chromatography eluting with 10-100% ethyl acetate in hexane

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

Procedure: To a solution of 4-[(phenylmethyl)oxy]-1H-indazole (D1) (280 mg, 1.25 mmol) in dichloromethane (20 mL) was added {3,5-difluoro-4-[(phenylmethyl)oxy]phenyl}boronic acid {DE patent application 4236105} (660 mg, 2.50 mmol), pyridine (0.202 mL, 2.50 mmol), copper acetate (340 mg, 1.88 mmol) and powdered 4A molecular sieves (500 mg). The reaction mixture was stirred at room temperature in the presence of air for 6 days. Celite was added to the mixture then the mixture was filtered through a pad of celite and then the filtrate was washed with water. After separation of the layers, the aqueous phase was re-extracted with dichloromethane. The combined organic layers were dried over magnesium sulphate, filtered and concentrated. The product was purified by silica gel chromatography eluting with 5-100% ethyl acetate in hexane to yield the title compound (D35 (257 mg). Celite was added to the mixture the mixture was filtered through a pad of celite the filtrate was washed with water After separation of the layers the aqueous phase was re-extracted with dichloromethane The combined organic layers were dried over magnesium sulphate filtered concentrated The product was purified by silica gel chromatography eluting with 5-100% ethyl acetate in hexane