2,3-Dihydroxybutanedioic Acid → HCID 57081700, compound

HRID 1603283Notes

Reaction equation

HRID 1603283 reaction equation
[OH:1][CH2:2][C:3]([CH2:5][CH:6]([O:26][Si:27]([C:30]([CH3:33])([CH3:32])[CH3:31])([CH3:29])[CH3:28])[CH2:7][CH2:8][C@H:9]([C@@H:11]1[C@:19]2([CH3:20])[CH:14]([CH:15]([O:21][Si:22]([CH3:25])([CH3:24])[CH3:23])[CH2:16][CH2:17][CH2:18]2)[CH2:13][CH2:12]1)[CH3:10])=[CH2:4].C(O)(=O)C(C(C(O)=O)O)[OH:36]>ClCCl.CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].[Ti+4]>[O:1]1[C@@:3]([CH2:4][OH:36])([CH2:5][CH:6]([O:26][Si:27]([C:30]([CH3:32])([CH3:31])[CH3:33])([CH3:29])[CH3:28])[CH2:7][CH2:8][C@H:9]([C@@H:11]2[C@:19]3([CH3:20])[CH:14]([CH:15]([O:21][Si:22]([CH3:23])([CH3:24])[CH3:25])[CH2:16][CH2:17][CH2:18]3)[CH2:13][CH2:12]2)[CH3:10])[CH2:2]1

Participants

5

Reactant 2

HCID 8752,3-Dihydroxybutanedioic AcidHCID 57153383HCID 57153383, compound

Product 1

HCID 57081700HCID 57081700, compoundYield 94%

Reagents, catalysts & solvents 2

HCID 11026Titanium isopropoxideCatalystHCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-20 °C

Procedure

A 20 ml amount of dichloromethane was placed in a 200 ml eggplant-shaped flask, 1.36 ml of titanium tetraisopropoxide was added, then the solution was cooled to -20° C. and stirred. Thereafter, 1.05 g of D(-)-diethyl tartrate dissolved in 5 ml of dichloromethane and the solution stirred at -25° C. for 20 minutes was placed and then, 2.14 g of the compound (4-10), (7R)-2-hydroxymethyl-4-(t-butyldimethylsilyloxy)-7-[(1R, 7aR)-octahydro-4-trimethylsilyloxy-7a-methyl-1H-inden-1-yl]-octene, dissolved in 10 ml of dichloromethane, was added, then the solution was stirred for 30 minutes. Further, 4.3 ml of t-butyldiperoxide was added and the solution was stirred at the same temperature for 30 minutes. The reaction solution was poured into 20 ml of a 10% aqueous solution of tartaric acid, the solution was stirred at that temperature for 30 minutes and at room temperature for 1 hour, then separation was performed and extraction performed from the aqueous layer by dichloromethane. The organic layer was washed by a 10% aqueous solution of tartaric acid and saturated saline and was dried over anhydrous magnesium sulfate. After filtration by Celite, the solvent was distilled off under reduced pressure, the obtained residue was dissolved in 50 ml of ether, 18 ml of 1N sodium hydroxide was added, then the solution was stirred under ice cooling for 1 hour. After separation, extraction was performed from the aqueous layer by ether. The organic layer was washed with saturated saline, then was dried over anhydrous magnesium sulfate, then filtered by Celite. The filtrate was concentrated under reduced pressure to obtain 2.40 g of a crude product. This was purified by a silica gel column (IR-60, 200 g, hexane/ethyl acetate=15/1 to 4/1) to obtain the desired product (4-11), (7R, 2R)-1,2-epoxy-2-hydroxymethyl-4-(t-butyldimethylsilyloxy)-7-[(1R,7aR)-octahydro-4-trimethylsilyloxy-7a-methyl-1H-inden-1-yl]-octane in an amount of 2.08 g (yield 94%).

Workup

  1. stirringthe solution stirred at -25° C. for 20 minutes
  2. additionwas added
  3. stirringthe solution was stirred for 30 minutes
  4. additionFurther, 4.3 ml of t-butyldiperoxide was added
  5. stirringthe solution was stirred at the same temperature for 30 minutes
  6. stirringthe solution was stirred at that temperature for 30 minutes and at room temperature for 1 hour
  7. customseparation
  8. extractionextraction
  9. washThe organic layer was washed by a 10% aqueous solution of tartaric acid and saturated saline
  10. dry with materialwas dried over anhydrous magnesium sulfate
  11. filtrationAfter filtration by Celite
  12. distillationthe solvent was distilled off under reduced pressure
  13. dissolutionthe obtained residue was dissolved in 50 ml of ether
  14. addition18 ml of 1N sodium hydroxide was added
  15. stirringthe solution was stirred under ice cooling for 1 hour
  16. customAfter separation, extraction
  17. washThe organic layer was washed with saturated saline
  18. dry with materialwas dried over anhydrous magnesium sulfate
  19. filtrationfiltered by Celite
  20. concentrationThe filtrate was concentrated under reduced pressure
  21. customto obtain 2.40 g of a crude product
  22. customThis was purified by a silica gel column (IR-60, 200 g, hexane/ethyl acetate=15/1 to 4/1)

Sources & evidence

ORD record
ord-9166b0580f0243549761186535527145
Source dataset
uspto-grants-1999_11
Patent number
US05986112

Reaction notes

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