p-Toluenesulfonic acid → HCID 9794426, 화합물

To a solution of (R)-(+)-binaphthol (7.9 mg, 0.0275 mmol) in CH2Cl2 (0.5 mL) was added a solution of Ti(OiPr)4 (3.8 uL, 3.6 mg, 0.0125 mmol) in CH2Cl2 (0.5 mL). Upon stirring at room temperature for 5-10 h, the reaction mixture was concentrated and dried using a vacuum pump (ca. 0.5 h). The catalyst was then dissolved in Et2O (1 mL) and cooled in an ice bath. To this solution was added a solution of racemic 1-benzoyloxy-1,2-epoxycyclohexane (0.109 g, 0.5 mmol) in Et2O (1 mL). After stirring at 0° C. for 1 h, the reaction mixture was quenched with saturated NaHCO3 solution (4 mL) and poured into a mixture of ether (20 mL) and saturated NaHCO3 solution (10 mL). The organic layer was washed with water and brine, dried (Na2SO4), and rapidly filtered through a plug of silica gel (ca. 10 g) (pre-treated with 5% Et3N in hexane and washed thoroughly with hexane to remove Et3N before use). The silica gel was further washed with Et2O (10 mL). The combined ether solutions were concentrated to give a residue. Upon drying under vacuum for 1 h, the mixture was dissolved in CH2Cl2 (4 mL) followed by addition of anhydrous p-TsOH (8.6 mg, 0.05 mmol). After stirring at room temperature for 20 min, the mixture was rapidly filtered through a plug of silica gel (ca. 10 g) (without Et3N treatment) followed by washing with ether (2×10 mL). The combined solutions were concentrated to give (R)-2-benzoyloxycyclohexanone as a white solid (0.0845 g, 78% yield, 93% ee).

1. concentrationthe reaction mixture was concentrated
2. customdried
3. customa vacuum pump (ca. 0.5 h)
4. dissolutionThe catalyst was then dissolved in Et2O (1 mL)
5. temperaturecooled in an ice bath
6. stirringAfter stirring at 0° C. for 1 h
7. customthe reaction mixture was quenched with saturated NaHCO3 solution (4 mL)
8. additionpoured into a mixture of ether (20 mL) and saturated NaHCO3 solution (10 mL)
9. washThe organic layer was washed with water and brine
10. dry with materialdried (Na2SO4)
11. filtrationrapidly filtered through a plug of silica gel (ca. 10 g) (
12. additionpre-treated with 5% Et3N in hexane
13. washwashed thoroughly with hexane
14. customto remove Et3N before use)
15. washThe silica gel was further washed with Et2O (10 mL)
16. concentrationThe combined ether solutions were concentrated
17. customto give a residue
18. customUpon drying under vacuum for 1 h
19. dissolutionthe mixture was dissolved in CH2Cl2 (4 mL)
20. stirringAfter stirring at room temperature for 20 min
21. filtrationthe mixture was rapidly filtered through a plug of silica gel (ca. 10 g) (without Et3N treatment)
22. washby washing with ether (2×10 mL)
23. concentrationThe combined solutions were concentrated

ORD 기록

ord-c7bc1f595fe147319191719fea44c7f1

출처 데이터셋

uspto-grants-2004_02

DOI

10.6084/m9.figshare.5104873.v1

특허 번호

US06686483B2