反应详情

温度

-78 °C

To a −78° C. solution of 2.5 g (13.7 mmol) of 3-hydroxypropane-1,2-diyl dinitrate in 20 mL dichloromethane was added 1.36 g (4.57 mmol) of triphosgene followed by 1.22 mL (15.10 mmol) of pyridine. The resulting mixture was stirred for 5 min at −78° C. then warmed to rt for 15 min upon which the solution turned from cloudy to clear. The above solution was then transferred slowly to a −78° C. solution of 5.64 g (13.04 mmol) (2Z)-4-{[tert-butyl(dimethyl)silyl]oxy}-2-[4-(methylsulfonyl)phenyl]-3-phenylbut-2-en-1-ol and 1.11 mL (13.73 mmol) pyridine in 20 mL of dichloromethane. After complete addition, the reaction mixture was warmed to 0° C. and stirred for an additional 25 min. The reaction was then quenched with NH4Cl (aq) and the organic layer separated, dried (Na2SO4), filtered and concentrated in vacuo to give a yellow oil. Purification by flash chromatography over silica gel (10-80% EtOAc/hexane) afforded 3.73 g of the title compound as an oil. 1H NMR (500 MHz, acetone-d6): δ 7.72 (d, 2H), 7.38 (d, 2H), 7.18-7.08 (m, 5H), 5.79-5.75 (m, 1H), 5.35 (s, 2H), 5.05 (dd, 1H), 4.87 (dd, 1H), 4.80 (s, 2H), 4.66 (dd, 1H), 4.49 (dd, 1H), 3.05 (s, 3H), 0.84 (s, 9H), 0.01 (s, 6H).

1. temperaturethen warmed to rt for 15 min upon which the solution
2. customwas then transferred slowly to a −78° C.
3. additionAfter complete addition
4. temperaturethe reaction mixture was warmed to 0° C.
5. stirringstirred for an additional 25 min
6. customThe reaction was then quenched with NH4Cl (aq)
7. customthe organic layer separated
8. dry with materialdried (Na2SO4)
9. filtrationfiltered
10. concentrationconcentrated in vacuo
11. customto give a yellow oil
12. customPurification by flash chromatography over silica gel (10-80% EtOAc/hexane)