Br[C:2]1[CH:3]=[C:4]([C:16]([NH:18][CH2:19][C:20]2[C:21](=[O:28])[NH:22][C:23]([CH3:27])=[CH:24][C:25]=2[CH3:26])=[O:17])[C:5]2[CH:6]=[N:7][N:8]([CH:11]3[CH2:15][CH2:14][CH2:13][CH2:12]3)[C:9]=2[CH:10]=1.[I-].[Na+].C1CCN2C(=NCCC2)CC1.[CH3:42][C:43]([OH:47])([C:45]#[CH:46])[CH3:44]>[Zn].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1COCC1.CCOC(C)=O.O.CS(C)=O>[CH:11]1([N:8]2[C:9]3[CH:10]=[C:2]([C:46]#[C:45][C:43]([OH:47])([CH3:44])[CH3:42])[CH:3]=[C:4]([C:16]([NH:18][CH2:19][C:20]4[C:21](=[O:28])[NH:22][C:23]([CH3:27])=[CH:24][C:25]=4[CH3:26])=[O:17])[C:5]=3[CH:6]=[N:7]2)[CH2:15][CH2:14][CH2:13][CH2:12]1To a 10 mL microwave vial containing a mixture of 6-bromo-1-cyclopentyl-N-[(4,6-dimethyl-2-oxo-1,2-dihydro-3-pyridinyl)methyl]-1H-indazole-4-carboxamide (0.12 g, 0.271 mmol), sodium iodide (8.11 mg, 0.054 mmol) and zinc (3.54 mg, 0.054 mmol) were added DMSO (2.5 mL), TEA (0.075 mL, 0.541 mmol), and DBU (0.082 mL, 0.541 mmol). The suspension was stirred and degassed with N2 for 5 min. Next added in 2-methyl-3-butyn-2-ol (0.131 mL, 1.353 mmol) and Pd(Ph3P)4 (0.031 g, 0.027 mmol). The reaction vial was sealed and stirred with heating at 85° C. (heat block) for 3 h. The mixture was then diluted into water and 20% THF/EtOAc. The contents were stirred and the layers were separated. The organic layer was washed with brine, dried over MgSO4, filtered through Celite, and concentrated in vacuo. The residue was dried on hi-vacuum pump overnight. The crude product was purified by silica gel chromatography (eluent: 5-80% gradient chloroform (containing 10% 2M ammonia in methanol) in DCM). The collected product was purified by reverse phase HPLC (Gradient B: 15-75%; A: Water+0.1% TFA. B: CH3CN+0.1% TFA). The product was suspended in 10% MeOH/CHCl3. Next added 0.5 g Silicycle carbonate resin and stirred for 15 min. After standing for 10 min, the contents were filtered through celite and concentrated in vacuo. The product was further concentrated from DCM and MTBE and then dried in hi-vac oven at 45° C. overnight. The title compound was collected as a white solid (38 mg, 30%); 1H NMR (400 MHz, DMSO-d6) δ ppm 1.47-1.52 (m, 6H), 1.64-1.73 (m, 2H), 1.80-1.91 (m, 2H), 1.92-2.02 (m, 2H), 2.06-2.15 (m, 5H), 2.18-2.23 (m, 3H), 4.28-4.38 (m, 2H), 5.25 (quin, J=7.07 Hz, 1H), 5.52 (s, 1H), 5.84-5.91 (m, 1H), 7.54 (d, J=1.01 Hz, 1H), 7.93 (s, 1H), 8.35 (s, 1H), 8.60 (t, J=4.93 Hz, 1H), 11.51 (br. s., 1H); LC-MS (ES) m/z=446.9 [M+H]
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