Cesium carbonate → HCID 57542017, compound

HRID 2422308Notes

Reaction equation

HRID 2422308 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:19]=[CH:20][CH:21]=1)[CH2:5][O:6][C:7]1[CH:12]=[CH:11][C:10]([CH2:13][CH2:14][C:15]([O:17]C)=[O:16])=[CH:9][CH:8]=1.[CH2:22]([NH:29][CH2:30][CH3:31])[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.C(=O)([O-])[O-].[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1(C)C=CC=CC=1>[CH2:22]([N:29]([CH2:30][CH3:31])[C:2]1[CH:3]=[C:4]([CH:19]=[CH:20][CH:21]=1)[CH2:5][O:6][C:7]1[CH:12]=[CH:11][C:10]([CH2:13][CH2:14][C:15]([OH:17])=[O:16])=[CH:9][CH:8]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Participants

6

Reactant 4

HCID 10796Cesium carbonateHCID 84352N-EthylbenzylamineHCID 634876Binap, (A+-)-HCID 23136270Methyl 4-[(3-bromophenyl)methoxy]benzenepropanoate

Product 1

HCID 57542017HCID 57542017, compoundYield 13%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of methyl 3-[4-[(3-bromobenzyl)oxy]phenyl]propanoate (0.30 g, 0.86 mmol), benzyl(ethyl)amine (0.20 mL, 1.29 mmol), cesium carbonate (0.39 g, 1.20 mmol), tris(dibenzylidenacetone)dipalladium (0) (0.031 g, 0.034 mmol), rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.032 g, 0.052 mmol) and toluene (6 mL) was stirred under a nitrogen atmosphere at 80° C. for 16 hrs. The reaction mixture was cooled, washed with water and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. Then the residue was dissolved in a mixed solution of methanol (4 mL) and tetrahydrofuran (6 mL), 1N aqueous sodium hydroxide solution (1.8 mL) was added, and the mixture was stirred at room temperature for 2 hrs. The reaction mixture was adjusted to pH 7 with 1N hydrochloric acid, and separated and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=2/1-1/2) to give the title compound (42 mg, yield 13%) as yellow crystals. MS (APCI−): 388 (M−H).

Workup

  1. temperatureThe reaction mixture was cooled
  2. washwashed with water and saturated brine
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. dissolutionThen the residue was dissolved in a mixed solution of methanol (4 mL) and tetrahydrofuran (6 mL), 1N aqueous sodium hydroxide solution (1.8 mL)
  6. additionwas added
  7. stirringthe mixture was stirred at room temperature for 2 hrs
  8. customseparated
  9. extractionextracted with ethyl acetate
  10. washThe organic layer was washed with water and saturated brine
  11. dry with materialdried over magnesium sulfate
  12. concentrationconcentrated under reduced pressure
  13. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate=2/1-1/2)

Sources & evidence

ORD record
ord-84231f9e630d4d4a854cd1285b9b3853
Source dataset
uspto-grants-2011_06
Patent number
US07960369B2

Reaction notes

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