Acetaldehyde → 1-chloroethyl (5R)-5,6-bis(nitrooxy)hexanoate

Participants

Reaction Steps

To a dichloromethane (10 mL) solution of (5R)-5,6-bis(nitrooxy)hexanoic acid (292 mg, 1.22 mmol) was added oxalyl chloride (0.54 mL, 6.12 mmol), followed by a few drops of N,N-dimethylformamide. After bubbling has stopped, the reaction mixture was concentrated in vacuo to afford a yellow slurry, which was redissolved in dichloromethane (5 mL). This solution was added to a mixture of zinc chloride (166 mg, 1.22 mmol) and acetaldehyde (0.15 mL, 2.66 mmol) in dichloromethane (5 mL) at 0° C. The reaction mixture turned cloudy immediately. It was warmed up to room temperature, stirred for 1 hour, and concentrated in vacuo to afford the crude product. Chromatography over silica eluting with ethyl acetate/hexanes afforded the diastereomeric 1-chloroethyl (5R)-5,6-bis(nitrooxy)hexanoate as a colorless liquid. 1H NMR (500 MHz, CDCl3) δ 6.54 (q, J=5.8 Hz, 1H, D1), 6.54 (q, J=5.8 Hz, 1H, D2), 5.25-5.35 (m, 1H), 4.76 (dd, J=3.1, 13.0 Hz, 1H, D1), 4.76 (dd, J=3.0, 12.8 Hz, 1H, D2), 4.49 (dd, J=6.5, 12.9 Hz, 1H, D1), 4.49 (dd, J=6.4, 13.1 Hz, 1H, D2), 2.4-2.5 (m, 2H), 1.7-1.9 (m, 7H).

Provenance & Evidence