反应详情

To a stirred solution of 3-ethyl-3-(6-thiophen-2-yl-hexyloxymethyl)oxetane (6.0 g, 21.28 mmol) in dry THF (70 ml) was added n-butyllithium (2.5 M in hexanes, 8.10 ml, 21.28 mmol) dropwise at −78° C. under nitrogen. After complete addition, the mixture was allowed to warm to room temperature, with stirring, over 2 h, followed by the addition of pinacol boronate (3.96 g, 21.28 mmol). The resultant mixture was stirred overnight at room temperature. The reaction was quenched with water, and the reaction mixture was extracted with ethyl acetate (3×70 ml). The combined organic extracts were washed with water, brine, and dried over sodium sulphate. The solvent was removed under reduced pressure and the residue was purified by column chromatography on silica, eluting with petroleum ether/ethyl acetate (9:1), to afford the product as a yellow oil (6.28 g, 72%). 1H NMR (300 MHz, CDCl3): δ (ppm) 7.45 (d, J=3.4 Hz, 1H, Ar—H), 6.85 (d, J=3.4 Hz, 1H, Ar—H), 4.44 (d, J=5.8 Hz, 2H, OCH2), 4.36 (d, J=5.8 Hz, 2H, OCH2), 3.51 (s, 2H, OCH2), 3.45 (t, J=6.4 Hz, 2H, OCH2), 2.83 (t, J=7.6 Hz 2H, ArCH2), 1.32-1.77 (m, 22H, CH2 and CH3), 0.88 (t, J=7.4 Hz, 3H, CH3); δ (ppm) 153.5 (quat.), 145.6 (quat.), 137.3 (CH), 125.9 (CH), 83.9 (quat.), 78.6 (OCH2), 73.4 (OCH2), 71.5 (OCH2), 43.4 (quat.), 31.6 (CH2), 30.1 (CH2), 29.4 (CH2), 28.8 (CH2), 26.8 (CH2), 25.9 (CH2), 24.8 (CH3), 8.2 (CH3); MS (m/e): 408 (M+, 0.5%), 223 (27), 165 (30), 141 (35), 123 (100), 97 (52).

1. additionAfter complete addition
2. customThe reaction was quenched with water
3. extractionthe reaction mixture was extracted with ethyl acetate (3×70 ml)
4. washThe combined organic extracts were washed with water, brine
5. dry with materialdried over sodium sulphate
6. customThe solvent was removed under reduced pressure
7. customthe residue was purified by column chromatography on silica
8. washeluting with petroleum ether/ethyl acetate (9:1)