Hydrochloric Acid → HCID 131723139, compound

HRID 277443Notes

Reaction equation

HRID 277443 reaction equation
[BH4-].[Na+].C(O)(=O)[C@@H]([C@H](C(O)=O)O)O.[O:13]=[C:14]([C@@H:20]([O:28][SiH2:29][C:30]([CH3:33])([CH3:32])[CH3:31])[CH:21]=[CH:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])[CH2:15][C:16]([O:18][CH3:19])=[O:17].Cl.[Cl-].[Na+]>C1COCC1.C(OCC)(=O)C>[OH:13][C@@H:14]([C@@H:20]([O:28][SiH2:29][C:30]([CH3:31])([CH3:33])[CH3:32])[CH:21]=[CH:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])[CH2:15][C:16]([O:18][CH3:19])=[O:17]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 5234Sodium ChlorideHCID 444305L-Tartaric acidHCID 4311764Sodium borohydrideHCID 131723140HCID 131723140, compound

Product 1

HCID 131723139HCID 131723139, compoundYield 89%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-20 °C

Procedure

NaBH4 (2.03 g, 53.72 mmol) was added in portions to a solution of L-tartaric acid (8.06 g, 53.72 mmol) in dry THF (125 ml), and the suspension thus obtained was heated at reflux temperature for 2.75 h and then cooled to −20° C. A solution of methyl (4S)-3-oxo-4-tert-butylsilyloxyundec-5-enoate (5.38 g, 11.55 mmol) in dry THF (75 ml) was then added dropwise, the temperature remaining at −20° C. After 43 h, hydrochloric acid (1M, 125 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 89% (4.77 g, 10.20 mmol).

Workup

  1. customthe suspension thus obtained
  2. temperaturewas heated
  3. temperatureat reflux temperature for 2.75 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-b251dc53c7d14ad89bfca1e11f1f4cb4
Source dataset
uspto-grants-2002_03
Patent number
US06355822B1

Reaction notes

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