[H-].[Na+].[OH:3][CH:4]1[CH2:9][CH2:8][N:7]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[CH2:6][CH2:5]1.Cl[C:18]1[CH:23]=[C:22]([C:24]2([OH:28])[CH2:27][O:26][CH2:25]2)[CH:21]=[C:20]([C:29]([F:32])([F:31])[F:30])[N:19]=1.[Cl-].[NH4+]>O1CCCC1.O>[OH:28][C:24]1([C:22]2[CH:21]=[C:20]([C:29]([F:32])([F:31])[F:30])[N:19]=[C:18]([O:3][CH:4]3[CH2:5][CH2:6][N:7]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[CH2:8][CH2:9]3)[CH:23]=2)[CH2:25][O:26][CH2:27]1To sodium hydride (60% in mineral oil, 0.20 g, 4.9 mmol) in a dry flask was added tetrahydrofuran (20 mL), followed by tert-butyl 4-hydroxypiperidine-1-carboxylate (0.98 g, 4.9 mmol, Aldrich). After stirring for 1 hour at room temperature, a solution of 3-[2-chloro-6-(trifluoromethyl)pyridin-4-yl]oxetan-3-ol (0.31 g, 1.2 mmol, from Step 1) in tetrahydrofuran (11 mL) was introduced. The reaction was stirred at ambient temperature for 2 hours, followed by heating to 65° C. overnight. The reaction was cooled to room temperature and water was added, followed by saturated ammonium chloride to adjust the pH to between 7 and 8. The product was extracted with two portions of DCM. The combined organic extracts were dried over sodium sulfate, decanted and concentrated. The product was purified by flash chromatography, eluting with a gradient from 0-20% EtOAc in hexanes, on a 40 g silica gel column to afford 0.17 g of desired product (yield 30%). 1H NMR (400 MHz, CDCl3) δ 7.58 (d, J=1.3 Hz, 1H), 7.22-7.15 (m, 1H), 5.28 (tt, J=7.6, 3.7 Hz, 1H), 4.91 (d, J=7.6 Hz, 2H), 4.77 (d, J=6.9 Hz, 2H), 3.72 (ddd, J=12.5, 6.6, 3.9 Hz, 2H), 3.32 (ddd, J=13.8, 8.0, 3.7 Hz, 2H), 1.98 (ddt, J=13.6, 7.1, 3.6 Hz, 2H), 1.73 (ddt, J=16.5, 8.1, 3.9 Hz, 2H), 1.46 (s, 9H). 19F NMR (376 MHz, CDCl3) δ −68.78 (s). LCMS (M+Na)+: 441.1.
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