[Br:1][C:2]1[CH:7]=[CH:6][N:5]2[N:8]=[C:9]([NH2:11])[N:10]=[C:4]2[CH:3]=1.ClC(Cl)(Cl)C(Cl)(Cl)Cl.C(N(CC)CC)C.CP(C)C.[CH3:31][C:32]1[N:36]=[C:35]([N:37]2[CH2:42][CH2:41][C:40](=O)[CH2:39][CH2:38]2)[S:34][N:33]=1.[B][B][B][B][B][B][B][B][B][B].C([O-])(O)=O.[Na+]>C1COCC1.CO>[Br:1][C:2]1[CH:7]=[CH:6][N:5]2[N:8]=[C:9]([NH:11][CH:40]3[CH2:39][CH2:38][N:37]([C:35]4[S:34][N:33]=[C:32]([CH3:31])[N:36]=4)[CH2:42][CH2:41]3)[N:10]=[C:4]2[CH:3]=1To a suspension of 7-bromo-[1,2,4]triazolo[1,5-a]pyridin-2-amine (prepared in analogy to example 66a-b starting from 4-bromo-pyridin-2-ylamine) (250 mg, 1.17 mmol) and hexachloroethane (333 mg, 1.41 mmol) under argon in dry THF (12.5 mL) was added triethylamine (356 mg, 491 μL, 3.52 mmol) and the mixture was heated to 50° C. for 10 minutes. Trimethylphosphine (1 M in THF, 1.41 mL, 1.41 mmol) was added. The reaction mixture was stirred at room temperature for 0.5 h, then 1-(3-methyl-1,2,4-thiadiazol-5-yl)piperidin-4-one (278 mg, 1.41 mmol) was added and the mixture heated in the microwave to 150° C. for 30 minutes. To the reaction mixture a solution of decaborane (143 mg, 153 μL, 1.17 mmol) in dry methanol (3 mL) was added and stirred at for 3 hours at room temperature. Further decaborane (34.4 mg, 36.6 μL, 282 μmol) in dry methanol (1.00 mL) was added. The reaction mixture was heated to 60° C. for 12 hours. Further decaborane (17 mg) dissolved in methanol (1 mL) was added and heated to 70° C. for 3 hours. Aqueous NaHCO3 solution was added and the aqueous phase was extracted with CH2Cl2, the organic layers were combined, dried over Na2SO4, filtered and the solvents were evaporated. The residue was purified by flash chromatography (silica gel, 70 g, 0% to 15% MeOH/NH4OH (9:1) in dichloromethane). The title compound was obtained as off-white solid (300 mg, 65%).
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