Ethyl bromoacetate → Ethyl 2-(6-methoxynaphthalen-2-yl)acetate

HRID 467447Notes

Reaction equation

HRID 467447 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[CH:9]=[C:8](B(O)O)[CH:7]=[CH:6]2.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.[O-]P([O-])([O-])=O.[K+].[K+].[K+].[CH2:46]([O:48][C:49](=[O:52])[CH2:50]Br)[CH3:47]>CC([O-])=O.CC([O-])=O.[Pd+2].CCOC(C)=O.O.C1COCC1>[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[CH:9]=[C:8]([CH2:50][C:49]([O:48][CH2:46][CH3:47])=[O:52])[CH:7]=[CH:6]2

Participants

9

Reactant 4

HCID 7748Ethyl bromoacetateHCID 62657Potassium Phosphate, TribasicHCID 80271Tri-o-tolylphosphineHCID 46416926-Methoxy-2-naphthaleneboronic acid

Product 1

HCID 11265053Ethyl 2-(6-methoxynaphthalen-2-yl)acetateYield 76.3%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

Into a 1 L round bottomed flask containing THF (335 mL) was added 6-methoxynaphthalen-2-ylboronic acid (20.15 g, 99.7 mmol, 1.2 eq), Pd(OAc)2 (563 mg, 2.51 mmol, 0.03 eq), tri-o-tolylphosphine (2.3 g, 7.56 mmol, 0.09 eq), K3PO4 (89 g, 419 mmol, 5 eq), and ethylbromoacetate (9.2 mL, 82.6 mmol, 1 eq). The resulting mixture was stirred for 24 h at room temperature. Water and EtOAc were added to the reaction and the mixture was stirred for 1 h. The layers were separated and both were saved. The aqueous layer was extracted with EtOAc. The organic layers were combined, washed with brine, dried over anhydrous sodium sulfate, filtered, and evaporated to afford a crude material, which was subjected to silica gel chromatography (gradient elution 0% to 20% EtOAc in hexanes) to afford ethyl 2-(6-methoxynaphthalen-2-yl)acetate (15.4 g, 76%) as a white, crystalline solid.

Workup

  1. stirringthe mixture was stirred for 1 h
  2. customThe layers were separated
  3. extractionThe aqueous layer was extracted with EtOAc
  4. washwashed with brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. customevaporated
  8. customto afford a crude material, which
  9. washwas subjected to silica gel chromatography (gradient elution 0% to 20% EtOAc in hexanes)

Sources & evidence

ORD record
ord-b71003e9bdeb4494a04d03a4eb2f327d
Source dataset
uspto-grants-2014_01
Patent number
US08623818B2

Reaction notes

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