反应详情

To a solution of (1R,10R,11S,16S)-3,5-dimethoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene (Compound No. 22) (3.75 g, 10 mmol) in CH2Cl2 (200 mL) was added BBr3 (1.0 M in CH2Cl2, 60 mL, 60 mmol) dropwise at 0° C., and the resulting mixture was stirred at room temperature for 48 h, then concentrated to dryness. Water (100 mL) was added at 0° C., followed by EtOAc (500 mL). The organic layer was separated, washed with brine (2×50 mL), dried (Na2SO4), and concentrated. Purification by chromatography on silica gel (Hexanes/EtOAc, 3:1) followed by dilution with MeOH, concentration and trituration with water gave (1R,10R,11S,16S)-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene-3,5-diol (Compound No. 26) (620 mg, 18%) as an off-white solid. 1H NMR (CDCl3): δ 6.18 (d, 1H), 5.90 (d, 1H), 4.70 (s, 1H), 4.42 (s, 1H), 3.30 (m, 1H), 2.90 (m, 1H), 2.76 (m, 1H), 1.84-1.40 (m, 8H), 1.39 (s, 3H), 1.20-1.00 (m, 2H), 0.96 (s, 3H), 0.95 (m, 1H), 0.85 (s, 3H), 0.85 (s, 3H). MS m/z 345 (C21H30O2S−H+).

1. concentrationconcentrated to dryness
2. additionWater (100 mL) was added at 0° C.
3. customThe organic layer was separated
4. washwashed with brine (2×50 mL)
5. dry with materialdried (Na2SO4)
6. concentrationconcentrated
7. customPurification by chromatography on silica gel (Hexanes/EtOAc, 3:1)
8. concentrationfollowed by dilution with MeOH, concentration and trituration with water