6-bromo-4-methoxypyrazolo[1,5-a]pyridine-3-carbonitrile (50.0 mg, 0.198 mmol), 1-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (61.9 mg, 0.298 mmol), tri-t-butylphosphonium tetrafluoroborate (5.8 mg, 0.02 mmol), tris(dibenzylideneacetone)dipalladium (0) (9.1 mg, 9.9 μmol), and potassium fluoride (38.0 mg, 0.655 mmol) were suspended in DMF (2 ml) and sparged with argon for 10 minutes. The mixture was heated to 100° C. for 2 h. The reaction mixture was cooled to ambient temperature, diluted in ethyl acetate, washed with saturated aqueous sodium hydrogen carbonate and brine then dried over sodium sulfate, filtered and concentrated. The residue was purified by preparative HPLC Reverse phase (C-18), eluting with Acetonitrile/Water+0.05%. The fractions containing product were combined and diluted in ethyl acetate, then washed with aqueous sodium bicarbonate and dried over sodium sulfate. The solution was filtered and concentrated under reduced pressure to give an off-white solid. The residue was further purified by column chromatography on silica gel (methanol/dichloromethane gradient) to give 4-methoxy-6-(1-methyl-1H-pyrazol-4-yl)pyrazolo[1,5-a]pyridine-3-carbonitrile as an off-white solid. 1H NMR (500 MHz, DMSO-d6) δ 8.86 (s, 1H); 8.53 (s, 1H); 8.36 (s, 1H); 8.08 (s, 1H); 7.26 (s, 1H); 4.05 (s, 3H); 3.87 (s, 3H). LRMS (ESI) calculated for C13H12N5O [M+H]+, 254.1; found 254.1.
