[C:1]([NH2:6])(=[O:5])[CH:2]([CH3:4])[CH3:3].C(Cl)(=O)[C:8](Cl)=[O:9].[CH3:13][N:14]1[CH:18]=[C:17]([C:19]2[CH:24]=[C:23]([O:25][C:26]3[CH:27]=[CH:28][C:29]([NH2:36])=[N:30][C:31]=3[C:32]([F:35])([F:34])[F:33])[CH:22]=[CH:21][N:20]=2)[CH:16]=[N:15]1.CCN(C(C)C)C(C)C.C(Cl)(=O)C(C)C>ClCCCl.O1CCOCC1.C(Cl)Cl.[Ag]OC#N.CCOC(C)=O>[CH3:13][N:14]1[CH:18]=[C:17]([C:19]2[CH:24]=[C:23]([O:25][C:26]3[CH:27]=[CH:28][C:29]([NH:36][C:8]([NH:6][C:1](=[O:5])[CH:2]([CH3:4])[CH3:3])=[O:9])=[N:30][C:31]=3[C:32]([F:35])([F:34])[F:33])[CH:22]=[CH:21][N:20]=2)[CH:16]=[N:15]1A suspension of Example B7 (0.021 g, 0.246 mmol) in DCE (3 mL) was treated with oxalyl chloride (0.022 mL, 0.246 mmol), stirred at RT for 5 min, then heated at 80° C. for 1 h. The mixture was cooled to RT, added drop-wise to a solution of 5-((2-(1-methyl-1H-pyrazol-4-yl)pyridin-4-yl)oxy)-6-(trifluoromethyl)pyridin-2-amine (0.055 g, 0.164 mmol) and DIEA (0.172 mL, 0.984 mmol) in dioxane (3 mL) and stirred at RT overnight. A solution of silver cyanate (0.246 g, 1.640 mmol) in DCM (3 mL) was treated with isobutyryl chloride (0.035 g, 0.328 mmol), stirred at RT for 2 h, then added to the DCE mixture and stirred at RT for 2 h. A second suspension of Example B7 (140 mg) in DCE (4 mL) was treated with oxalyl chloride (0.15 mL), heated at 80° C. for 2 h, cooled to RT, added to the original reaction mixture and stirred at RT overnight. The mixture was treated with EtOAc and the solids removed via filtration through diatomaceous earth. The filtrate was washed with satd. NaHCO3 (2×) and the combined organics were dried over Na2SO4, concentrated to dryness and purified via silica gel chromatography (MeOH/EtOAc) to afford N-((5-((2-(1-methyl-1H-pyrazol-4-yl)pyridin-4-yl)oxy)-6-(trifluoromethyl)pyridin-2-yl)carbamoyl)isobutyramide (33 mg, 45%) as a light brown solid. 1H NMR (400 MHz, DMSO-d6): δ 11.28 (s, 1H), 10.97 (s, 1H), 8.40 (d, J=5.7 Hz, 1H), 8.34 (d, J=9.1 Hz, 1H), 8.28 (s, 1H), 7.98-7.97 (m, 2H), 7.29 (d, J=2.5 Hz, 1H), 6.78 (dd, J=5.7, 2.5 Hz, 1H), 3.84 (s, 3H), 2.72-2.63 (m, 1H), 1.10 (d, J=6.8 Hz, 6H); MS (ESI) m/z: 449.2 (M+H+).
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