Acetic Acid → 3-[4-(Methoxycarbonyl)bicyclo[2.2.2]oct-1-yl]propanoic acid

HRID 22855Notes

Reaction equation

HRID 22855 reaction equation
C([O:8][C:9](=[O:24])/[CH:10]=[CH:11]/[C:12]12[CH2:19][CH2:18][C:15]([C:20]([O:22][CH3:23])=[O:21])([CH2:16][CH2:17]1)[CH2:14][CH2:13]2)C1C=CC=CC=1.C(O)(=O)C>C(OCC)(=O)C.CO.[Pd]>[CH3:23][O:22][C:20]([C:15]12[CH2:18][CH2:19][C:12]([CH2:11][CH2:10][C:9]([OH:24])=[O:8])([CH2:17][CH2:16]1)[CH2:13][CH2:14]2)=[O:21]

Participants

5

Reactant 2

HCID 176Acetic AcidHCID 22591724methyl 4-[(1E)-3-(benzyloxy)-3-oxoprop-1-en-1-yl]bicyclo[2.2.2]octane-1-carboxylate

Product 1

HCID 225917033-[4-(Methoxycarbonyl)bicyclo[2.2.2]oct-1-yl]propanoic acid

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 21584119Ethylacetate methanolSolvent

Procedure

Diester 11-2 (0.625 g, 1.90 mmol) was dissolved in a 1:1 mixture of ethyl acetate/methanol (30 mL), placed under nitrogen atmosphere, then treated with 10% Pd/C (500 mg) and 0.1 mL of acetic acid. The reaction was placed under hydrogen atmosphere and stirred vigorously for 2 hr. The resulting solution was filtered through celite and the solvent was removed under reduced pressure. The residue was partitioned between 200 mL of ethyl acetate and 200 mL of 1 N NaOH solution. The aqueous layer was separated and neutralized, then extracted three times with 50 mL of methylene chloride. The combined organic layers were dried over magnesium sulfate and the solvent was removed under reduced pressure to afford 3-[4-(methoxycarbonyl)bicyclo[2.2.2]oct-1-yl]propanoic acid (11-3). 1H NMR (500 MHz, CDCl3): δ 3.62 (3H, s), 2.20 (2H, broad t, J=9 Hz), 1.75 (6H, m), 1.47 (2H, broad t, J=9 Hz), 1.38 (6H, m) ppm.

Workup

  1. filtrationThe resulting solution was filtered through celite
  2. customthe solvent was removed under reduced pressure
  3. customThe residue was partitioned between 200 mL of ethyl acetate and 200 mL of 1 N NaOH solution
  4. customThe aqueous layer was separated
  5. extractionextracted three times with 50 mL of methylene chloride
  6. dry with materialThe combined organic layers were dried over magnesium sulfate
  7. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-677e47164eaf44268b7c91bfb27b0180
Source dataset
uspto-grants-2005_02
Patent number
US06849636B2

Reaction notes

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