反应详情

To a solution of 9.70 g (22.0 mmol) of enone 13 in 60 mL of THF at -23° C. was added dropwise a solution of 11.1 g (34.6 mmol) of (-)-B-chlorodiisopino-campheylborane in 30 mL of THF. After 4 h, the reaction was quenched by the dropwise addition of 5 mL of methanol and then warmed to room temperature. After pouring into 200 mL of a 2/1 mixture of ethyl acetate/saturated NH4Cl, the layers were separated, and the aqueous phase was extracted with ethyl acetate (2×100 mL). Combined organic layers were dried over MgSO4, filtered, concentrated, and the residue was chromatographed on silica gel eluting with ethyl acetate/hexanes, 3/2, to afford 4.7 g (48%) of 14 as a white solid, m.p. 101.0°-102.5° C. 1H NMR δ 8.05-7.95 (m, 2 H), 7.62-7.40 (m, 3 H), 7.18 (t, J=8.0 Hz, 1 H), 7.0-6.92 (m, 1 H), 6.85 (t, J=2.1 Hz, 1 H), 6.77-6.70 (m, 1 H), 5.85 (d of d, J=6.2, 15.5 Hz, 1 H), 5.72 (d of d, J=4.5, 15.5 Hz, 1 H), 5.30 (q, J=5.8 Hz, 1 H), 5.12-5.04 (m, 1 H), 4.58-4.48 (m, 1 H), 3.92 (d of d, J=3.5, 9.3 Hz, 1 H), 3.80 (d of d, J=7.3, 9.4 Hz, 1 H), 2.9-2.2 (m, 8 H).

1. customthe reaction was quenched by the dropwise addition of 5 mL of methanol
2. additionAfter pouring into 200 mL of a 2/1 mixture of ethyl acetate/saturated NH4Cl
3. customthe layers were separated
4. extractionthe aqueous phase was extracted with ethyl acetate (2×100 mL)
5. dry with materialCombined organic layers were dried over MgSO4
6. filtrationfiltered
7. concentrationconcentrated
8. customthe residue was chromatographed on silica gel eluting with ethyl acetate/hexanes, 3/2