S(C)C.[OH:4][C:5]1[CH:14]=[C:13]2[C:8]([CH2:9][C@H:10]([C:15]([NH:17][C@H:18]([CH2:22][N:23]3[CH2:28][CH2:27][C@:26]([C:30]4[CH:35]=[CH:34][CH:33]=[C:32]([OH:36])[CH:31]=4)([CH3:29])[C@@H:25]([CH3:37])[CH2:24]3)[CH:19]([CH3:21])[CH3:20])=O)[NH:11][CH2:12]2)=[CH:7][CH:6]=1.Cl.CCOCC>C1COCC1.CO>[OH:36][C:32]1[CH:31]=[C:30]([C@:26]2([CH3:29])[CH2:27][CH2:28][N:23]([CH2:22][C@@H:18]([NH:17][CH2:15][C@H:10]3[CH2:9][C:8]4[C:13](=[CH:14][C:5]([OH:4])=[CH:6][CH:7]=4)[CH2:12][NH:11]3)[CH:19]([CH3:21])[CH3:20])[CH2:24][C@@H:25]2[CH3:37])[CH:35]=[CH:34][CH:33]=1A solution of 2M BH3.SMe2 in THF (0.495 mL 0.99 mmol) was added drop-wise to a −20° C.-solution of 14 (46 mg, 0.099 mmol) in 5 mL of dry THF. The reaction refluxed overnight. It was again cooled to −20° C. and 0.647 mL of MeOH was added. Contents stirred at room temperature for one hour. At room temperature, 1M HCl in ether (0.142 mL, 0.142 mmol) was added, and stirred for 30 minutes. The solvent was then removed under reduced pressure. The oil was then dissolved in 3:1 CH2Cl2:THF. Then, enough sat'd NaHCO3 was added to increase the pH to 10. The organic layer was separated and set aside. The aqueous layer was extracted five times with 3:1 CH2Cl2:THF. The organic layer was dried over sodium sulfate, and the solvent was removed under reduced pressure, yielding a yellowish foam. The crude product (0.03 g) was purified by silica preparative thin layer chromatography using a solvent gradient, starting with 25% (CHCl3:MeOH:NH4OH, 80:18:2) in CHCl3 then 40%, and finally 65%. This afforded 0.006 g of (3R)-3-{[((1S)-1-{[(3R,4R)-4-(3-hydroxyphenyl)-3,4-dimethyl-1-piperidinyl]methyl}-2-methylpropyl)amino]methyl}-1,2,3,4-tetrahydro-7-isoquinolinol (19). 1H-NMR (MeOH): 7.12(t, J=5.1 Hz, 1H), 6.90 (d, J=4.1 Hz, 1H), 6.8(d, J=3.9 Hz, 1H), 6.76 (d, J=1.1 Hz, 1h), 6.61 (dd, J=5.8,2.2 Hz, 2H), 6.48 (d, J=1.2 Hz, 1H), 2.88-2.43 (m, 16H), 2.4-1.8 (m, 2H), 1.67 (d, J=13 Hz, 1H), 1.34 (s, 3H), 1.01 (d, J=6.9 Hz, 3H), 0.95 (d, J=6.9 Hz, 3H), 0.81 (d, J=3.4 Hz, 3H). LRMS (ES) m/z 452.3 (M+H)+.
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