Cesium carbonate → (3-Bromo-5-oxo-5,6,7,8-tetrahydro-naphthalen-1-yloxy)-acetic acid tert-butyl ester

HRID 2383999Notes

Reaction equation

HRID 2383999 reaction equation
[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([CH2:6][CH2:7][CH2:8][C:9]2=[O:12])=[C:4]([OH:13])[CH:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].Br[CH2:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23]>C(#N)C>[C:25]([O:24][C:22](=[O:23])[CH2:21][O:13][C:4]1[C:5]2[CH2:6][CH2:7][CH2:8][C:9](=[O:12])[C:10]=2[CH:11]=[C:2]([Br:1])[CH:3]=1)([CH3:28])([CH3:27])[CH3:26]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 79177tert-Butyl bromoacetateHCID 591925237-bromo-5-hydroxy-3,4-dihydro-2H-naphthalen-1-one

Product 1

HCID 59192521(3-Bromo-5-oxo-5,6,7,8-tetrahydro-naphthalen-1-yloxy)-acetic acid tert-butyl esterYield 65%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a suspension of 7-bromo-5-hydroxy-3,4-dihydro-2H-naphthalen-1-one (XIb, 158 mg, 0.65 mmol) and cesium carbonate (431 mg, 1.31 mmol) in acetonitrile (5 mL) was added tert-butyl bromoacetate (XII, 261 mg, 1.31 mmol) at room temperature under nitrogen. The resulting suspension was stirred for 15 h at room temperature and then concentrated under vacuum. The residue was diluted with water (10 mL) and ethyl acetate (20 mL). The aqueous layer was separated and extracted with ethyl acetate (20 mL), and the combined organic extracts were washed with brine solution (50 mL), then dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo to give the crude product. Chromatography using an ISCO (40 g) column, (gradient elution with 5-25% ethyl acetate in hexanes) provided (3-bromo-5-oxo-5,6,7,8-tetrahydro-naphthalen-1-yloxy)-acetic acid tert-butyl ester (150 mg, 64%) as a white solid: ES(+)-HRMS m/e calcd. for C16H19O4Br (M+Na)+377.0359, obsd. 377.0358.

Workup

  1. concentrationconcentrated under vacuum
  2. additionThe residue was diluted with water (10 mL) and ethyl acetate (20 mL)
  3. customThe aqueous layer was separated
  4. extractionextracted with ethyl acetate (20 mL)
  5. washthe combined organic extracts were washed with brine solution (50 mL)
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customto give the crude product
  10. washan ISCO (40 g) column, (gradient elution with 5-25% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-8d9b0ebff9bd41fdb81d9e27c9b61341
Source dataset
uspto-grants-2012_09
Patent number
US08263656B2

Reaction notes

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