Hydrochloric Acid → HCID 131723139, compound

HRID 277442Notes

Reaction equation

HRID 277442 reaction equation
[BH4-].[Na+].C(O)(=O)[C@H]([C@@H](C(O)=O)O)O.[CH3:13][O:14][C:15](=[O:33])[CH2:16][C:17](=[O:32])[C@@H:18]([O:26][SiH2:27][C:28]([CH3:31])([CH3:30])[CH3:29])[CH:19]=[CH:20][CH2:21][CH2:22][CH2:23][CH2:24][CH3:25].Cl.[Cl-].[Na+]>C1COCC1.C(OCC)(=O)C>[OH:32][C@@H:17]([C@@H:18]([O:26][SiH2:27][C:28]([CH3:29])([CH3:31])[CH3:30])[CH:19]=[CH:20][CH2:21][CH2:22][CH2:23][CH2:24][CH3:25])[CH2:16][C:15]([O:14][CH3:13])=[O:33]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 5234Sodium ChlorideHCID 439655D-Tartaric acidHCID 4311764Sodium borohydrideHCID 131723140HCID 131723140, compound

Product 1

HCID 131723139HCID 131723139, compoundYield 93%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-20 °C

Procedure

NaBH4 (2.42 g, 64 mmol) was added in portions to a solution of D-tartaric acid (9.6 g, 64 mmol) in dry THF (150 ml), and the suspension thus obtained was heated at reflux temperature for 2.5 h and then cooled to −20° C. A solution of (4S)-methyl-3-oxo-4-tert-butylsilyloxyundec-5-enoate (7.54 g, 16 mmol) in dry THF (75 ml) was then added dropwise, the temperature remaining at −20° C. After 40 h, hydrochloric acid (1M, 150 ml) was added to the reaction mixture, on account of which the temperature increased to room temperature. The mixture was stirred for a further 15 minutes. Ethyl acetate (500 ml), followed by solid sodium chloride, was then introduced until the saturation point was reached. The aqueous phase was separated off and extracted with a further 200 ml of ethyl acetate. The organic phases were combined, washed twice with 150 ml in each case of saturated sodium bicarbonate solution and then with 100 ml of a saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by column chromatography (90:10 to 80:20), petroleum ether:ethyl acetate), by means of which methyl (3R, 4S)-3-hydroxy-4-tert-butylsilyloxyundec-5-enoate was obtained as a colorless oil in a yield of 93% (6.97 g, 14.7 mmol).

Workup

  1. customthe suspension thus obtained
  2. temperaturewas heated
  3. temperatureat reflux temperature for 2.5 h
  4. customremaining at −20° C
  5. temperatureincreased to room temperature
  6. additionwas then introduced until the saturation point
  7. customThe aqueous phase was separated off
  8. extractionextracted with a further 200 ml of ethyl acetate
  9. washwashed twice with 150 ml in each case of saturated sodium bicarbonate solution
  10. dry with materialwith 100 ml of a saturated sodium chloride solution, dried over sodium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated under reduced pressure
  13. customThe crude product was purified by column chromatography (90:10 to 80:20), petroleum ether

Sources & evidence

ORD record
ord-be7b1e24ff29482c995cc3b94b307803
Source dataset
uspto-grants-2002_03
Patent number
US06355822B1

Reaction notes

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