[CH3:1][C:2]([CH3:4])=O.[NH2:5][CH2:6][C:7]1[CH:12]=[C:11]([O:13][C:14]2[CH:19]=[CH:18][C:17]([NH:20][C:21]3[CH:26]=[C:25]([C:27]4[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=4)[N:24]=[C:23]([NH2:33])[N:22]=3)=[CH:16][CH:15]=2)[CH:10]=[CH:9][N:8]=1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>C(Cl)Cl.C[O-].[Ti+4].C[O-].C[O-].C[O-]>[CH:2]([NH:5][CH2:6][C:7]1[CH:12]=[C:11]([O:13][C:14]2[CH:15]=[CH:16][C:17]([NH:20][C:21]3[CH:26]=[C:25]([C:27]4[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=4)[N:24]=[C:23]([NH2:33])[N:22]=3)=[CH:18][CH:19]=2)[CH:10]=[CH:9][N:8]=1)([CH3:4])[CH3:1]Acetone (11.51 mg, 0.20 mmol), N4-(4-{[2-(aminomethyl)pyridin-4-yl]oxy}phenyl)-6-phenylpyrimidine-2,4-diamine (80 mg, 0.21 mmol, Example 39) and titanium (IV) methoxide (68.2 mg, 0.40 mmol) were suspended in CH2Cl2 (5 mL) and stirred at rt for 24 h. Sodium triacetoxyborohydride (105 mg, 0.50 mmol) was added into the reaction mixture and the mixture was stirred at rt for another 24 h. The mixture was filtered through a Celite® pad and washed with CH2Cl2. A small amount of Celite® was added to the filtrate and 5 mL of water was added to quench the reaction. After it was stirred for 20 min, the CH2Cl2 was removed in vacuo. The residue was taken up in ethyl acetate and washed with 1N NaOH (2×) and water (3×). The organic layer was concentrated and purified by Prep-TLC (MeOH) to give 36 mg (42.2%) of the title product as a white solid. 1H NMR (CD3OD) δ 8.35 (d, 1H), 7.82 (d, 2H), 7.00 (d, 2H), 7.44 (m, 3H), 7.08 (m, 2H), 7.01 (s, 1H), 6.82 (m, 1H), 6.46 (s, 1H), 3.81 (s, 2H), 2.80 (m, 1H), 1.10 (d, 6H); MS ES 427 (M+H)+, calcd 427, RT=2.59 min; TLC (MeOH)Rf=0.38.
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