3-Phenylprop-2-En-1-Ol → ((2R,3R)-3-phenyloxiran-2-yl)methanol

Temperature

-20 °C

To a solution of diisopropyl D-tartrate (6 mL, 28 mmol) in methylene chloride (800 mL) at −10° C. under nitrogen was added 4A molecular sieves (15 g), titanium isopropoxide (5.9 mL, 20 mmol), and cinnamyl alcohol (27 g, 200 mmol). The mixture was allowed to age for 40 minutes at −10° C., after which time it was cooled to −20° C., and treated in a dropwise fashion with a solution of tert-butyl hydroperoxide (TBHP, ˜450 mmol) in isooctane. After 18 hours at −30 to −15° C., the reaction mixture was treated with a 30% aqueous solution of sodium hydroxide (5 mL) and diethyl ether (100 mL). The cold bath was removed and the mixture was allowed to warm to ˜10° C. Magnesium sulfate (anhydrous, 15 g) was added and the mixture was stirred for 20 minutes. After the solids settled, the solution was filtered through a pad of silica gel, and washed with ether (50 mL). The filtrate was concentrated in vacuo and toluene was added to azeotropically remove the unreacted TBHP. The residue was then purified using a silica gel column (hexane:ethyl acetate/3:1) and the purified product was crystallized from hexane/ethyl acetate to yield [(2R,3R)-3-phenyloxiran-2-yl]methanol as white crystal (18 g, 60%, 98.2% ee). MS (ESI) m/z 151.

1. waitAfter 18 hours at −30 to −15° C.
2. customThe cold bath was removed
3. temperatureto warm to ˜10° C
4. additionMagnesium sulfate (anhydrous, 15 g) was added
5. filtrationthe solution was filtered through a pad of silica gel
6. washwashed with ether (50 mL)
7. concentrationThe filtrate was concentrated in vacuo and toluene
8. additionwas added
9. customto azeotropically remove the unreacted TBHP
10. customThe residue was then purified
11. customthe purified product was crystallized from hexane/ethyl acetate

ORD record

ord-e0879733d7274bfebc5494ea9a2bcfab

Source dataset

uspto-grants-2008_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07414052B2