1,1'-Carbonyldiimidazole → HCID 71116093、化合物

反応式

[O:1]1[C:3]2([CH2:8][CH2:7][CH2:6][CH:5]([C:9]([O:11][CH3:12])=[O:10])[CH2:4]2)[CH2:2]1.[CH2:13]([NH2:18])[C:14]([CH3:17])([CH3:16])[CH3:15].C1N=CN([C:24](N2C=NC=C2)=[O:25])C=1>CO>[CH2:13]([N:18]1[CH2:2][C:3]2([CH2:8][CH2:7][CH2:6][CH:5]([C:9]([O:11][CH3:12])=[O:10])[CH2:4]2)[O:1][C:24]1=[O:25])[C:14]([CH3:17])([CH3:16])[CH3:15]

参加物

実験手順

To a solution containing racemic methyl 1-oxaspiro[2.5]octane-5-carboxylate (34.2 g, 201 mmol), dissolved in MeOH (540 mL) was added neopentyl amine (18.4 g, 211 mmol). The reaction was heated at reflux for 20 h. The reaction mixture was cooled to rt and concentrated to an oil. The crude material was dissolved in 1,4-dioxane (540 mL) and treated with CDI (42.3 g, 261 mmol). The reaction was again heated at reflux. After 14 h, the reaction was concentrated to a thick oil, taken up in water, and acidified to pH 3. The product was extracted into DCM (5×300 mL). The combined organics were washed with concentrated aqueous H3PO4 solution followed by brine. The organics were then dried over sodium sulfate, filtered, and concentrated to a waxy white solid. This solid was purified on a 330 g silica gel column (0-60% EtOAc/hexanes, 30 min gradient; 100 mL/min elution; 254 nm detection) to provide the title compound (40.8 g, 69.7%) as a white solid. 1H NMR (400 MHz, CDCl3) δ 3.69 (s, 3H), 3.38 (dd, J=8.78, 13.05 Hz, 2H), 3.01 (dd, J=14.05, 25.35 Hz, 2H), 2.17-2.28 (m, 1H), 2.02-2.12 (m, 1H), 1.98 (dd, J=2.13, 13.68 Hz, 1H), 1.71-1.86 (m, 2H), 1.54-1.65 (m, 2H), 1.29-1.47 (m, 2H), 0.97 (s, 9H).