[C:1]([C:5]1[CH:9]=[C:8]([NH:10][C:11]2[CH:20]=[C:19](Cl)[CH:18]=[CH:17][C:12]=2[C:13]([O:15][CH3:16])=[O:14])[N:7]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=2[CH3:28])[N:6]=1)([CH3:4])([CH3:3])[CH3:2].[CH2:29](B(O)O)[CH3:30].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.[F-].[K+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O1CCOCC1>[C:1]([C:5]1[CH:9]=[C:8]([NH:10][C:11]2[CH:20]=[C:19]([CH2:29][CH3:30])[CH:18]=[CH:17][C:12]=2[C:13]([O:15][CH3:16])=[O:14])[N:7]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=2[CH3:28])[N:6]=1)([CH3:4])([CH3:3])[CH3:2]To a mixture of methyl 2-{[3-tert-butyl-1-(2-methylphenyl)-1H-pyrazol-5-yl]amino}-4-chlorobenzoate (Example 242, 50 mg, 0.13 mmol), ethylboronic acid (18.56 mg, 0.26 mmol), Pd2(dba)3 (5.8 mg, 0.006 mmol), tris(tert-butyl)phosphine (2.54 mg, 0.013 mmol), and potassium fluoride (14.6 mg, 0.25 mmol) was added dioxane (1 mL). The resulting solution was degassed under argon for 30 min and then heated to 110° C. for 16 h. The reaction mixture was then cooled to rt. The residue was diluted with ethyl acetate and filtered through a silica gel plug. The solvent was removed under reduced pressure, and the crude product was purified by HPLC purification using gradient elution from 30 to 100% acetonitrile in water to afford 39.8 mg (81%) of the title compound. 1H NMR (300 MHz, CD2Cl2) δ 9.23 (s, 1H), 7.74 (d, 1H), 7.23-7.29 (m, 4H), 7.03 (s, 1H), 6.57 (d, 1H), 6.09 (s, 1H), 3.69 (s, 3H), 2.55 (q, 2H), 2.06 (s, 3H), 1.30 (s, 9H), 1.15 (t, 3H). ES-MS m/z 392.2 (MH+); HPLC RT (min) 4.65.
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