Pyridine → 2,3-bis(nitrooxy)propyl (2Z)-4-{[tert-butyl(dimethyl)silyl]oxy}-2-[4-(methylsulfonyl)phenyl]-3-phenylbut-2-en-1-yl carbonate

Participants

Reaction Conditions

Reaction Steps

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).

Provenance & Evidence