1-azido-4-bromobenzene

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 3-Ethynyl-1H-indazole (6.0 g, 42.2 mmol) in Dioxane (60 mL) were added 4-Azidobromobenzene (Ukrorgsynthesis Ltd., 9.19 g, 46.4 mmol), D-(−)-Iso ascorbic acid sodium salt (0.83 g, 4.2 mmol) and a solution of CuSO4.5H2O (0.21 g, 0.8 mmol) in water (10 mL). The reaction mixture was heated at 80° C. for 3 days. After completion of the reaction, the reaction mixture was cooled to RT, diluted with ethyl acetate, washed with water and brine, dried over sodium sulfate and concentrated. The crude compound was recrystallized from methanol and dried under vacuum to afford the title compound as brown solid (9.0 g, 63%). 1H NMR (400 MHz, DMSO-d6) δ 13.36 (s, 1H), 9.36 (s, 1H), 8.35-8.33 (d, J=8.1 Hz, 1H), 8.06-8.02 (m, 2H), 7.86-7.82 (m, 2H), 7.61-7.59 (d, J=8.4 Hz, 1H), 7.45-7.41 (m, 1H), 7.26-7.22 (m, 1H). After completion of the reaction the reaction mixture was cooled to RT washed with water and brine dried over sodium sulfate concentrated The crude compound was recrystallized from methanol dried under vacuum

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The general click procedure was used substituting the following quantities using: 37 (60 mg, 0.17 mmol); 1-azido-4-bromobenzene (51 mg, 0.26 mmol); CuSO4 (4.4 mg, 0.03 mmol); NaAsc (22 mg, 0.11 mmol); TBTA (20.0 mg, 0.04 mmol); in t-BuOH/EtOH/H2O (2:2:1); afforded the 44 as a white solid (40 mg, 42.6%). 1H NMR (DMSO-d6, 400 MHz): δ 9.00-8.99 (d, 1H, J=1.66 Hz); 8.74-8.71 (t, 1H); 8.63-8.61 (d, 1H, J=8.22 Hz); 8.54 (s, 1H); 7.60-7.56 (d, 2H, J=14.85 Hz); 7.345-7.341 (d, 1H, J=1.63 Hz); 7.11-7.07 (d, 2H, J=14.85 Hz); 4.69-4.66 (q, 1H); 4.40-4.38 (d, 2H, J=5.59 Hz); 4.20-4.13 (m, 2H); 3.66-3.66 (d, 1H, J=1.73 Hz); 3.52-3.51 (d, 1H, J=1.73 Hz); 3.33-3.12 (m, 2H); 1.23-1.20 (t, 3H). 13C NMR (100 MHz, DMSO-d6): 170.57, 167.51, 165.36, 154.07, 153.27, 146.56, 139.39, 136.25, 122.30, 121.54, 117.51, 116.23, 61.97, 53.46, 52.99, 51.76, 34.75, 33.50, 14.32.