Compound A7

View in PubChem | MDL Molfile | ChemDraw

InChIKey VSOPSMFWKLBEDW-OHQAAIJDSA-N

Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.

Adrenosterone (107.3 mg, 0.357 mmol) was dissolved in concentrated sulfuric acid (1 mL) at room temperature before cooling to 0 °C. Sodium azide (70 mg, 1.072 mmol) was then added to the reaction slowly and the resulting reaction mixture was allowed to stir for 1 hour at 0 °C. After this time, ice was added to quench the reaction and stirring continued for an additional 3 minutes before being transferred to a separatory funnel and partitioned between brine and dichloromethane. Dichloromethane was used to extract the desired Schmidt products (3x). The organic layers were combined, dried with magnesium sulfate and concentrated under reduced pressure to give a crude white foam. The two products were purified via column chromatography using 100:0 to 95:5 ethyl acetate/methanol to afford 31.7 mg (28% yield) of lactam A6 as a white foam and 21.4 mg of enamide A7 (19% yield) as a white foam. M.p. 63-65 °C. ¹H NMR (CDCl₃, 500 MHz): δ 7.25 - 7.16 (br m, 1H), 5.88 (s, 1H), 5.58 (d, J = 5.8 Hz, 1H), 2.78 (ddd, J = 14.5, 6.5, 3.9 Hz, 1H), 2.47 (m, 2H), 2.36 - 2.06 (m, 8H), 2.03 - 1.87 (m, 3H), 1.88 (s, 3H), 1.27 (s, 3H), 1.19 (dq, J = 13.5, 4.0 Hz, 1H). ¹³C NMR (CDCl₃, 125 MHz): δ 198.5, 177.4, 156.2, 131.2, 128.9, 119.4, 115.8, 57.3, 46.3, 41.2, 36.7, 33.5, 32.9, 31.9, 31.7, 24.2, 21.6, 20.6, 12.7. HRMS(ESI): m/z calc. for C₁₉H₂₅N₂O₂ [M+H]⁺: 313.1916, found: 313.1918. IR (cm^-1 NaCl plates, thin film in CDCl₃): 3242 (b, m), 2928 (b, m), 2245 (m), 1660 (s), 1437 (m), 1380 (m).