反应详情

A solution of TBAF (3.98 mL of a 1M solution in THF, 3.98 mmol) was added to the bis-silyl ether 34 (1.41 g, 1.59 mmol) in THF (35 mL) at 0° C. (ice/acetone). The reaction mixture was allowed to warm to room temperature and after a further 30 minutes saturated NH4Cl (120 mL) was added. The aqueous solution was extracted with EtOAc (3×80 mL), washed with brine (80 mL), dried (MgSO4), filtered and evaporated in vacuo to give a dark orange oil which was purified by flash chromatography (97% CHCl3/MeOH) to provide the pure diol 35 as a light orange solid (0.98 g, 94%): [α]19D=−31.9° (c=0.09, CHCl3); 1H NMR (270 MHz, CDCl3) (Rotamers) δ 7.75 and 7.71 (s×2, 2Harom), 6.96 and 6.84 (s×2, 2Harom), 5.08, 5.02 and 4.88 (br s×3, 4H, NCH2C═CH2), 4.61-4.50 (m, 2H, NCHCH2OH), 4.35-4.33 (m, 4H, OCH2CH2CH2O), 4.02-3.65 (m, 14H, NCHCH2OH, NCH2C═CH2 and OCH3), 2.88-2.43 (m, 6H, NCH2C═CH2CH2 and OCH2CH2CH2O); 13C NMR (67.8 MHz, CDCl3) (Rotamers) δ 167.9 and 166.9 (NC═O), 154.9 and 154.3 (Cquat), 148.4 and 148.2 (Cquat), 143.3 and 142.6 (Cquat), 137.2 and 137.0 (Cquat), 127.6 and 127.3 (Cquat), 109.1 (C—Harom), 108.4 (NCH2C═CH2), 108.2 (C—Harom), 65.6 and 65.4 (OCH2CH2CH2O), 64.5 and 63.3 (NCHCH2OH), 60.5 and 60.0 (NCHCH2OH), 56.8 and 56.7 (OCH3), 52.9 (NCH2C═CH2), 35.0 and 34.3 (NCH2C═CH2CH2), 29.6 and 28.6 (OCH2CH2CH2O); MS (FAB) (Relative Intensity) 657 (M++1, 10), 639 (M-OH, 2), 612 (1), 544 (M-NCH2CCH2CH2CHCH2OH, 4), 539 (1), 449 (16), 433(9), 404 (8), 236 (32), 166 (65), 151 (81), 112 (82), 82 (100); IR (NUJOL7) 3600-3200 (br, OH), 2923, 2853, 2360, 1618, 1582, 1522 (NO2), 1459, 1408, 1375, 1335 (NO2), 1278, 1218, 1061, 908, 810, 757 cm−1.

1. additionwas added
2. extractionThe aqueous solution was extracted with EtOAc (3×80 mL)
3. washwashed with brine (80 mL)
4. dry with materialdried (MgSO4)
5. filtrationfiltered
6. customevaporated in vacuo
7. customto give a dark orange oil which
8. customwas purified by flash chromatography (97% CHCl3/MeOH)