Hydrogen Peroxide → Carvone oxide

Participants

Reaction Steps

Synthesis of epoxide 10 from S-(+)-carvone as illustrated in FIG. 3. A solution of 4 N NaOH (48 mL, 192.0 mmol, 0.3 equivalents) was slowly added to a solution of S-(+)-carvone (100.0 g, 665 mmol, 1.0 equivalent) in MeOH (1000 mL) at 0° C., followed by the dropwise addition of 35% hydrogen peroxide solution (70.0 mL, 792.6 mmol, 1.2 equivalents) over 3 hours. After the reaction was complete as established by TLC analysis, it was quenched by the slow addition of saturated Na2SO3 solution (200 mL) and extracted with CH2Cl2 (3×300 mL). The organic extracts were dried over Na2SO4 and concentrated to afford the carvone epoxide product which was used without further purification. A solution of this epoxide (101.8 g, 612.4 mmol, 1.0 equivalent) and PtO2 (0.72 g, 3.18 mmol, 0.095 equivalents) in EtOH (500 mL) was stirred under a hydrogen atmosphere (1 atm) at 25° C. for 12 hours. The reaction mixture was then filtered through a celite pad eluting with Et2O and concentrated. The crude product was purified by flash chromatography (silica gel, 5% EtOAc in hexane) to afford epoxide 10 (97.8 g, 87%, two steps) as a colorless oil. Rf=0.40 (silica gel, EtOAc-hexane, 1:10); FT-IR (neat) nmax 2959, 2873, 1708, 1466, 1438, 1369, 1111, 884, 814 cm-1.

Provenance & Evidence