反应详情

Alcohol 3 (51.1 mg, 0.3925 mmol) in 3 ml of CH2Cl2 was treated successively with DIPEA (102 μl, 0.5888 mmol, 1.5 eq), DMAP (1 crystal), and TBSCl (77 mg, 0.5103 mmol, 1.3 eq) and refluxed for 12 h. The solution was poured onto 20 ml of 0.2M pH 7 phosphate buffer and 30 ml of low boiling petroleum ether, shaken, and separated. The aqueous phase was extracted with petroleum ether (3×10 ml), washed with pH 7 buffer (1×10 ml), H2O (1×5 ml), brine (1×5 ml), dried over MgSO4, and concentrated to give 86.0 mg of 4 as a clear oil (89.6%). 1H NMR (CDCl3, 360.134 MHz) δ:3.57 (1H, d, J=11.15 Hz), 3.53 (1H, d, J=11.17 Hz), 2.82 (1H, t, J=5.70 Hz), 1.6-1.4 (4H, m), 1.25 (3H,s), 0.95 (3H, t, J=7.13 Hz), 0.87 (9H, s), 0.04 (3H, s), and (3H, s). 13C NMR (CDCl3, 90.55 MHz) δ:68.0, 61.0, 60.8, 30.2, 25.8, 19.7, 18.3, 14.1, 13.9, and -5.4. IR (thin film): 2959 (s), 2930 (s), 2859 (s), 1473 (m), 1464 (m), 1382 (w), 1362 (w), 1253 (m), 1103 (s), 838 (s), 778 (s), and 667 (w) cm-1. [δ]D=+4.9° (c=2.62, CH2Cl2).

1. temperaturerefluxed for 12 h
2. customseparated
3. extractionThe aqueous phase was extracted with petroleum ether (3×10 ml)
4. washwashed with pH 7 buffer (1×10 ml), H2O (1×5 ml), brine (1×5 ml)
5. dry with materialdried over MgSO4
6. concentrationconcentrated