Borane → HCID 53675379, compound

HRID 249555Notes

Reaction equation

HRID 249555 reaction equation
C(B(CC)CC)C.[OH:8][CH:9]([CH2:14][C:15](=[O:22])[CH2:16][C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:10]([O:12][CH3:13])=[O:11].B.[BH4-].[Na+]>C1COCC1.O.C(O)(=O)C.CO>[OH:8][CH:9]([CH2:14][CH:15]([OH:22])[CH2:16][C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:10]([O:12][CH3:13])=[O:11]

Participants

9

Reactant 4

HCID 6331BoraneHCID 7357TriethylboraneHCID 4311764Sodium borohydrideHCID 54285185HCID 54285185, compound

Product 1

HCID 53675379HCID 53675379, compoundYield 69%

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 887MethanolSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-55 °C

Procedure

A mixture of THF (2.5 ml), methanol (5 ml) and triethylborane (1M in THF) (12 ml) was stirred at a temperature from -50 to -60° C. for one hour in an argon atmosphere. A solution of 1-methyl 6-ethyl 2-hydroxy-4-oxoadipate (2.2 g, 10 mmol) in THF (2.5 ml) was dropwise added to the above borane solution at -60° C. After stirring at -78° C. for 60 minutes, sodium borohydride (378 mg, 10 mmol) was added in one portion, followed by stirring at -78° C. for 2 hours. After dropwise adding acetic acid (3 ml) to the reaction solution at -78° C., the solution was stirred for 15 minutes. After adding water (5 ml), THF was evaporated off. After adding ethanol (10 ml) and a 10 % hydrogen peroxide (1.5 ml) at room temperature, 1 N hydrochloric acid was added to adjust pH to 7, followed by stirring for one hour. After adding a 5 % aqueous solution of sodium sulfite (15 ml) and stirring the mixture at room temperature for 40 minutes, the mixture was extracted with methylene chloride and organic layers were combined, dried over sodium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (hexane:acetone=5:1) to give pure 1-methyl 6-ethyl 2,4-dihydroxyadipate (1.52 g, 6.9 mmol). Yield, 69 %.

Workup

  1. stirringAfter stirring at -78° C. for 60 minutes
  2. stirringby stirring at -78° C. for 2 hours
  3. customwas evaporated off
  4. additionAfter adding ethanol (10 ml)
  5. additiona 10 % hydrogen peroxide (1.5 ml) at room temperature, 1 N hydrochloric acid was added
  6. stirringby stirring for one hour
  7. additionAfter adding a 5 % aqueous solution of sodium sulfite (15 ml)
  8. stirringstirring the mixture at room temperature for 40 minutes
  9. extractionthe mixture was extracted with methylene chloride and organic layers
  10. dry with materialdried over sodium sulfate
  11. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-9eba337d7f9c4b2da4a9b0f375017daf
Source dataset
uspto-grants-1993_05
Patent number
US05214197

Reaction notes

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