Triethylamine → HCID 10922673, compound

To 1.88 g(8.38 mmol) of (3S,3aS,4R,4aS,8aR,9aS)-4-hydroxy-3-methyl-decahydronaphtho[2,3-c]furan-1(3H)-one in 200 ml of dehydrated ether solution were added dropwise 26.7 ml(3 equivalents) of diisobutylalumium hydride-hexane solution(0.94 M) at −78° C. under an atmosphere of argon. After stirring for about 1 hour at the same temperature, methanol-water mixed solution (10 ml+10 ml) was added dropwise slowly and the mixture was stirred for 1 hour at room temperature. Solvent was distilled off and 100 ml of ethyl acetate were added to the residue, which was filtered through celite, and the residue was washed with ethyl acetate(50 ml). Solvent was distilled off and 100 ml of saturated brine were added, which was extracted with methylene chloride(30 ml×3). The organic layer was dried over anhydrous magnesium sulfate, filtered and solvent was distilled off to obtain crude lactol form. This was dissolved into a mixed solution of 50 ml of dehydrated methanol with 50 ml of dehydrated methylene chloride, 1.55 ml(1.5 equivalents) of boron trifluoride-diethyl ether complex were added dropwise at −60° C. under an atmosphere of argon, and the mixture was stirred for about 12 hours while raising temperature naturally. To the reaction mixture were added 1.75 ml (1.5 equivalents) of triethylamine and, after stirring at room temperature, solvent was distilled of. To the residue was added 100 ml of cold dilute aqueous solution of sodium hydrogencarbonate, which was extracted with methylene chloride(30 ml×3). The organic layer was dried over anhydrous magnesium sulfate, filtered and solvent was distilled off. The residue was purified by means of silica gel column chromatography(hexane:ethyl acetate=2:1) to obtain 1.50 g of (1S,3S,3aS,4R,4aS,8aR,9aS)-4-hydroxy-1-methoxy-3-methyl-dodecahydronaphtho[2,3-c]furan (yield after two processes 74%).

1. additionwas added dropwise slowly
2. distillationSolvent was distilled off
3. addition100 ml of ethyl acetate were added to the residue, which
4. filtrationwas filtered through celite
5. washthe residue was washed with ethyl acetate(50 ml)
6. distillationSolvent was distilled off
7. addition100 ml of saturated brine were added
8. extractionwhich was extracted with methylene chloride(30 ml×3)
9. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
10. filtrationfiltered
11. distillationsolvent was distilled off
12. customto obtain crude lactol form
13. additionwere added dropwise at −60° C. under an atmosphere of argon
14. stirringthe mixture was stirred for about 12 hours
15. temperaturewhile raising temperature naturally
16. stirringafter stirring at room temperature
17. distillationsolvent was distilled of
18. additionTo the residue was added 100 ml of cold dilute aqueous solution of sodium hydrogencarbonate, which
19. extractionwas extracted with methylene chloride(30 ml×3)
20. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
21. filtrationfiltered
22. distillationsolvent was distilled off
23. customThe residue was purified by means of silica gel column chromatography(hexane:ethyl acetate=2:1)

ORD record

ord-ae0d2f0c72104e8eb79c3137eaf61dd4

Source dataset

uspto-grants-2002_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06392059B1