Br[C:2]1[CH:7]=[CH:6][C:5]([CH:8]([OH:13])[C:9]([F:12])([F:11])[F:10])=[CH:4][CH:3]=1.[C:14]([C:16]1[C:24]2[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=2)[NH:18][N:17]=1)#[CH:15].[N-:25]=[N+:26]=[N-:27].[Na+].CN[C@@H]1CCCC[C@H]1NC.[NH4+].[OH-]>CS(C)=O.O.[Cu](I)I>[F:10][C:9]([F:12])([F:11])[CH:8]([C:5]1[CH:6]=[CH:7][C:2]([N:25]2[CH:15]=[C:14]([C:16]3[C:24]4[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=4)[NH:18][N:17]=3)[N:27]=[N:26]2)=[CH:3][CH:4]=1)[OH:13]A mixture of 1-(4-bromophenyl)-2,2,2-trifluoroethan-1-ol (296 mg; 1.16 mmol; 1.1 eq.), 3-Ethynyl-1H-indazole (150 mg; 1.06 mmol; 1.0 eq.), sodium azide (75 mg; 1.16 mmol; 1.1 eq.), D-(−)-isoascorbic acid sodium salt (21 mg; 0.11 mmol; 0.1 eq.), copper iodide (20 mg; 0.11 mmol; 0.1 eq.) and trans-1,2-bis(methylamino)cyclohexane (22 mg; 0.16 mmol; 0.15 eq.) in DMSO (2.6 mL) and WATER (0.5 mL) was heated in a sealed tube at 70° C. for 48 h. The reaction mixture was poured into a solution of saturated NH4OH and extracted with DCM (twice). Combined organic phases were washed with brine, dried over magnesium sulfate, filtered and concentrated. Purification by preparative HPLC gave the title compound as a beige solid (100 mg, 26%). 1H NMR (DMSO) δ 13.38 (brs, 1H), 9.33 (s, 1H), 8.36 (dt, J=8.0 Hz, 1.0 Hz, 1H), 8.12 (d, J=8.7 Hz, 2H), 7.75 (d, J=8.7 Hz, 2H), 7.61 (dt, J=8.4 Hz, 1.0 Hz, 1H), 7.47-7.42 (m, 1H), 7.29-7.23 (m, 1H), 7.05 (bs, 1H), 5.34 (q, J=7.2 Hz, 1H). HPLC (max plot) 100.0%; Rt %3.83 min. UPLC/MS: (MS+) 360.4, (MS−) 358.4.
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