I[C:2]1[N:11]=[C:10]2[N:4]([CH2:5][CH2:6][C:7]3[CH:23]=[CH:22][CH:21]=[CH:20][C:8]=3[CH:9]2[O:12][CH:13]2[CH2:18][CH2:17][N:16]([CH3:19])[CH2:15][CH2:14]2)[CH:3]=1.O.[CH3:25][C:26]1[CH:31]=[CH:30][C:29](B(O)O)=[CH:28][CH:27]=1.C([O-])([O-])=O.[K+].[K+]>O1CCOCC1.CC([O-])=O.CC([O-])=O.[Pd+2].[CH-]1C(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=C1.[CH-]1C(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=C1.[Fe+2]>[CH3:19][N:16]1[CH2:17][CH2:18][CH:13]([O:12][CH:9]2[C:8]3[CH:20]=[CH:21][CH:22]=[CH:23][C:7]=3[CH2:6][CH2:5][N:4]3[C:10]2=[N:11][C:2]([C:29]2[CH:30]=[CH:31][C:26]([CH3:25])=[CH:27][CH:28]=2)=[CH:3]3)[CH2:14][CH2:15]1To a solution of 2-iodo-4-(1-methylpiperidin-4-yloxy)-9,10-dihydro-4H-3,10a-diaza-benzo[f]azulene (example 2) (50 mg, 0.12 mmole) in 1,4-dioxane (0.5 mL) are added water (0.1 mL), 4-methylbenzeneboronic acid (25 mg, 0.18 mmole), Pd(OAc)2 (1.4 mg, 6 μmmole), 1,1-bis(diphenylphosphino)ferrocene (3.3 mg, 6 μmmole) and K2CO3 (50 mg, 0.36 mmole). The vial is evacuated and filled with argon. The reaction mixture is stirred at 100° C. for 3.5 hours. Water is added to the reaction mixture, and the pH is adjusted to 9-10 by adding saturated Na2CO3 solution. The aqueous phase is extracted three times with AcOEt. The organic phase is dried over magnesium sulphate, filtered and the solvent is removed under reduced pressure. The residue is pre-purified by silica gel chromatography using (CH2Cl2:MeOH:NH4OH) as eluent with a gradient from (99:5:0.1) to (95:5:0.5). The residue is purified by preparative TLC eluting with (CH2Cl2:MeOH:NH4OH) (9:9:0.1) to give 4-(1-methylpiperidin-4-yloxy)-2-p-tolyl-9,10-dihydro-4H-3,10a-diaza-benzo[f]azulene.
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