C[O:2][C:3](=O)[CH2:4][C:5]1[CH:42]=[CH:41][C:40]([C:43]([F:46])([F:45])[F:44])=[CH:39][C:6]=1[CH2:7][CH2:8][C:9]1[C:14]([C:15]([F:18])([F:17])[F:16])=[CH:13][N:12]=[C:11]([NH:19][C:20]2[CH:25]=[CH:24][C:23]([CH:26]3[CH2:31][CH2:30][N:29]([C:32]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=O)[CH2:28][CH2:27]3)=[CH:22][CH:21]=2)N=1.O[Li].[OH2:50].C1C=CC2N(O)N=NC=2C=1.CCN=C=NCCCN(C)C.Cl.Cl.CCN(C(C)C)C(C)C.C(=O)([O-])[O-].[NH4+:87].[NH4+:88]>CO.O.C1COCC1.CCOC(C)=O>[NH2:87][C:3](=[O:2])[CH2:4][C:5]1[CH:42]=[CH:41][C:40]([C:43]([F:44])([F:45])[F:46])=[CH:39][C:6]=1[CH2:7][CH2:8][C:9]1[C:14]([C:15]([F:18])([F:17])[F:16])=[CH:13][N:12]=[C:11]([NH:19][C:20]2[CH:25]=[CH:24][C:23]([CH:26]3[CH2:31][CH2:30][N:29]([C:32]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:50])[CH2:28][CH2:27]3)=[CH:22][CH:21]=2)[N:88]=1A suspension of tert-butyl 4-(4-((4-(2-(2-methoxy-2-oxoethyl)-5-(trifluoromethyl)phenethyl)-5-(trifluoromethyl)pyrimidin-2-yl)amino)phenyl)piperidine-1-carboxylate (A61) (0.100 g, 0.150 mmol) and LiOH.H2O (0.051 g, 1.21 mmol) in MeOH (2 mL), water (2 mL) and THF (2 mL) was heated at 40° C. for 16 hours. In a separate flask, a suspension of tert-butyl 4-(4-((4-(2-(2-methoxy-2-oxoethyl)-5-(trifluoromethyl)phenethyl)-5-(trifluoromethyl)pyrimidin-2-yl)amino)phenyl)piperidine-1-carboxylate (A61) (0.070 g, 0.105 mmol) and LiOH.H2O (0.036 g, 0.858 mmol) in MeOH (2 mL), water (2 mL) and THF (2 mL) was heated at 40° C. for 16 hours. The resulting mixtures were combined and the volatiles were removed under reduced pressure. The resulting solid was dissolved in dry DMF (5 mL) and dry THF (5 mL) and HOBt (0.053 g, 0.398 mmol), EDCl.HCl (0.061 g, 0.398 mmol), DIPEA (0.260 mL, 1.53 mmol) and ammonium carbonate (0.144 g, 1.53 mmol) were added. The resulting mixture was stirred at room temperature for 16 hours then HOBt (0.053 g, 0.398 mmol), EDCl.HCl (0.061 g, 0.398 mmol), DIPEA (0.260 mL, 1.53 mmol) and ammonium carbonate (0.144 g, 1.53 mmol) were added and stirring was continued overnight. The resulting mixture was diluted with EtOAc, then washed with 10% aqueous NaHCO3. The organic layer was dried (MgSO4) and the volatiles were removed in vacuo. The resulting solid was adsorbed onto silica gel then purified by column chromatography (Biotage Isolera, SiO2 cartridge, 0-50% EtOAc in petroleum benzine 40-60° C.) to give the title compound A62 as a yellow solid (0.086 g, 43%); 1H NMR (400 MHz, CDCl3) δ 8.54 (s, 1H), 7.55-7.47 (m, 5H), 7.38 (d, J=8.3 Hz, 1H), 7.21 (d, J=8.5 Hz, 2H), 5.48-5.28 (m, 2H), 4.39-4.15 (m, 2H), 3.74 (s, 2H), 3.22-3.13 (m, 2H), 3.12-3.05 (m, 2H), 2.88-2.73 (m, 2H), 2.70-2.56 (m, 1H), 1.85-1.80 (m, 2H), 1.70-1.61 (m, 2H), 1.49 (s, 9H). LCMS-A: rt 6.646 min; m/z 652 [M+H]+.
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