反应详情

温度

60 °C

Compound 516A (17.42 mmoles, 5.000 g) was added to the reaction flask followed by the addition of zinc bromide (17.58 mmoles, 3.960 g) and then toluene (50.00 mL, 43.25 g) was added to the mixture. The resulting suspension was stirred for 20 min. Hexamethyldisilazane (26.35 mmoles, 5.560 mL, 4.253 g) was added to this suspension which was then heated to 60° C. for 4.5 h. The reaction mixture was diluted with EtOAc (25 mL) and then poured into a 1N HCl solution (30 mL) at 25° C. The organic phase was collected and the aqueous phase was extracted with EtOAc (15 mL). The organic phase was isolated, combined with the earlier organic phase and washed consecutively with saturated NaHCO3 (15 mL), a mixture of 1:1 water:brine solution (15 mL) and brine (15 mL). The resulting solution was dried over MgSO4, filtered and concentrated in vacuo to a 50 mL suspension. Heptane (125 mL) was added dropwise to this suspension with agitation. The resulting thicker suspension was filtered and washed with a mixture of 2:1 heptane:toluene (15 mL) and then heptane (15 mL) to give 4 g (85% yield) of compound 516B. HPLC: 100% at 2.11 min (retention time) (YMC S5 ODS column, 4.6×50 mm, eluting with 10-90% aqueous methanol over 4 min containing 0.2% phosphoric acid, 4 mL/min, monitoring at 220 nm).

1. customThe organic phase was collected
2. extractionthe aqueous phase was extracted with EtOAc (15 mL)
3. customThe organic phase was isolated
4. washwashed consecutively with saturated NaHCO3 (15 mL)
5. additiona mixture of 1:1 water
6. dry with materialThe resulting solution was dried over MgSO4
7. filtrationfiltered
8. concentrationconcentrated in vacuo to a 50 mL suspension
9. additionHeptane (125 mL) was added dropwise to this suspension with agitation
10. filtrationThe resulting thicker suspension was filtered
11. washwashed with a mixture of 2:1 heptane