Acetic Acid → Methyl (5Z,13E,15R)-9beta-chloro-11alpha,15-dihydroxy-16,16-dimethylprosta-5,13-dien-1-oate

HRID 1382533Notes

Reaction equation

HRID 1382533 reaction equation
COC(=O)C=CCCCC.[CH3:11][O:12][C:13](=[O:38])[CH2:14][CH2:15][CH2:16]/[CH:17]=[CH:18]\[CH2:19][C@H:20]1[C@H:24]([Cl:25])[CH2:23][C@@H:22]([OH:26])[C@@H:21]1/[CH:27]=[CH:28]/[C:29](=[O:37])[C:30]([CH3:36])([CH3:35])[CH2:31][CH2:32][CH2:33][CH3:34].[Cl-].[Ce+3].[Cl-].[Cl-].[BH4-].[Na+].C(O)(=O)C>CO>[CH3:11][O:12][C:13](=[O:38])[CH2:14][CH2:15][CH2:16]/[CH:17]=[CH:18]\[CH2:19][C@H:20]1[C@H:24]([Cl:25])[CH2:23][C@@H:22]([OH:26])[C@@H:21]1/[CH:27]=[CH:28]/[C@@H:29]([OH:37])[C:30]([CH3:36])([CH3:35])[CH2:31][CH2:32][CH2:33][CH3:34]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 24636Cerium(III) chlorideHCID 4311764Sodium borohydrideHCID 86742756(+/-)-(Z)-7-{(1R,2R,3R,5R)-5-chloro-2-[(E)-4,4-dimethyl-3-oxo-1-octenyl]-3-hydroxy-cyclopentyl}-5-heptenic acid methyl ester heptenic acid methyl ester

Product 1

HCID 13853250Methyl (5Z,13E,15R)-9beta-chloro-11alpha,15-dihydroxy-16,16-dimethylprosta-5,13-dien-1-oate

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A solution of 600 mg of IX in 25 ml of methanol is mixed with 60 mg of cerium(III) chloride with stirring and then 500 mg of sodium borohydride is added at -40° C. After 1 hour, thin-film chromatography checking shows a complete reduction. It is installed with 1 ml of glacial acetic acid, concentrated by evaporation in a vacuum, diluted with water and extracted several times with dichloromethane. The combined organic phases are washed with sodium bicarbonate solution and salt water, dried over magnesium sulfate and concentrated by evaporation in a vacuum. The residue is chromatographed on silica gel with dichloromethane/1-10% acetane. First 280 mg of XI is eluted as nonpolar component and then 295 mg of the desired epimer X, both as colorless oils.

Workup

  1. concentrationconcentrated by evaporation in a vacuum
  2. additiondiluted with water
  3. extractionextracted several times with dichloromethane
  4. washThe combined organic phases are washed with sodium bicarbonate solution and salt water
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated by evaporation in a vacuum
  7. customThe residue is chromatographed on silica gel with dichloromethane/1-10% acetane
  8. washFirst 280 mg of XI is eluted as nonpolar component

Sources & evidence

ORD record
ord-978bc160c1ac428b878612ee98813bfa
Source dataset
uspto-grants-1989_02
Patent number
US04806668

Reaction notes

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