tert-Butyl hydroperoxide → (2R-trans)-3-[3-(1-Dodecynyl)pbenyl]oxiranemethanol

Temperature

-20 °C

To a solution (−) diisopropyltartrate (524 mg) in dry dichloromethane (60 ml) and 4A molecular sieves (1 g) at −20° C. was added titanium(IV) isopropoxide (0.53 ml) followed by t-butylhydroperoxide (3.0M, isooctane) (20 ml). The reaction mixture was stirred for 20 mins at −20° C. and then a solution of trans-3-[3-(1-dodecynyl)phenyl]propene-1-ol (8.88 g) in dichloromethane (20 ml) was added slowly. The mixture was stirred for 1.5 hr and quenched with 25% aqueous sodium hydroxide (6 ml) followed by water (40 ml). The mixture was allowed to warm to room temperature, and was stirred for 30 min. The organic phase was separated, and the aqueous phase was extracted with dichloromethane. The organic extracts were combined, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated in vacuo. The residue was chromatographed over silica gel (eluted with ethyl acetate/Heptane/1:2). The appropriate fractions were collected and evaporated. The residue was crystallized from heptane to afford 6.5 g (69%) of product, mp 41-42° C. [α]D25 +33.1° (c. 0.725, chloroform).

1. stirringThe mixture was stirred for 1.5 hr
2. customquenched with 25% aqueous sodium hydroxide (6 ml)
3. temperatureto warm to room temperature
4. stirringwas stirred for 30 min
5. customThe organic phase was separated
6. extractionthe aqueous phase was extracted with dichloromethane
7. dry with materialdried over anhydrous magnesium sulfate
8. filtrationfiltered
9. concentrationthe filtrate was concentrated in vacuo
10. customThe residue was chromatographed over silica gel (eluted with ethyl acetate/Heptane/1:2)
11. customThe appropriate fractions were collected
12. customevaporated
13. customThe residue was crystallized from heptane

ORD record

ord-acb27c05124240d9b6b3c80be3be86ff

Source dataset

uspto-grants-2002_12

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06500849B1