Ethyl Acetate → [3-Bromo-5-(4-methoxy-benzyloxy)-phenyl]-pyridin-3-yl-amine

Participants

Reaction Conditions

Reaction Steps

An oven-dried flask was charged with (±)-BINAP (504 mg, 0.81 mmol), Pd2(dba)3 CHCl3-complex (278 mg, 0.27 mmol) and then flushed with argon. Degassed toluene (50 mL) was added and the solution was stirred for 10 min. A second oven-dried flask was charged with 3,5-dibromo-1-p-methoxy-benzyloxybenzene (20.0 g, 53.8 mmol), 3-aminopyridine (2.72 g, 26.9 mmol) and sodium tert-butanolate (3.61 g, 37.6 mmol) in degassed toluene (100 mL) and the mixture was heated to 90° C. The catalyst solution was then added to the mixture and the reaction mixture was stirred at 90° C. for 40 h. The reaction mixture was cooled to room temperature and brine (120 mL) and AcOEt (120 mL) were added and the mixture was filtered over Hyflo. The filtrate was transferred to a separatory funnel and the layers were separated. The aqueous layer was extracted with AcOEt (2×100 mL) and the layers were separated. The organic layer was washed with brine (2×80 mL), dried (Na2SO4) and concentrated to give the crude product. FC (SiO2, AcOEt/heptane 1:2→2:1) gave 7.96 (75%) of (3-p-methoxybenzyloxy-5-bromo-phenyl)-pyridin-3-yl-amine as yellow oil. 3,5-Dibromo-1-p-methoxy-benzyloxybenzene was recovered, repurified and can be reused.

Provenance & Evidence