1-Bromo-4-fluorobenzene → HCID 59505198, compound

HRID 1253757Notes

Reaction equation

HRID 1253757 reaction equation
C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.[C:47]([O:51][C:52]([N:54]1[CH2:59][CH2:58][C:57]2([CH2:64][CH2:63][NH:62][CH2:61][CH2:60]2)[CH2:56][CH2:55]1)=[O:53])([CH3:50])([CH3:49])[CH3:48].Br[C:66]1[CH:71]=[CH:70][C:69]([F:72])=[CH:68][CH:67]=1>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:47]([O:51][C:52]([N:54]1[CH2:59][CH2:58][C:57]2([CH2:64][CH2:63][N:62]([C:66]3[CH:71]=[CH:70][C:69]([F:72])=[CH:68][CH:67]=3)[CH2:61][CH2:60]2)[CH2:56][CH2:55]1)=[O:53])([CH3:50])([CH3:48])[CH3:49]

Participants

6

Reactant 3

HCID 99931-Bromo-4-fluorobenzeneHCID 634876Binap, (A+-)-HCID 15296367tert-Butyl 3,9-diazaspiro[5.5]undecane-3-carboxylate

Product 1

HCID 59505198HCID 59505198, compoundYield 43%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

BINAP (350 mg, 0.47 mmol) and Pd2 dba3 (317 mg, 1.57 mmol) was added to a mixture of 3,9-diazaspiro[5.5]undecane-3-carboxylic acid tert-butyl ester (2 g, 7.87 mmol), 1-bromo-4-fluoro-benzene (1.3 g, 7.87 mmol) and sodium tert-butylate (2.26 g, 23.61 mmol) in toluene (25 ml) and the reaction mixture was degassed under argon for 20 minutes and heated under reflux for 4 h. The mixture was then diluted with ethyl acetate, stirred for 15 minutes and filtered over Celite. The reaction mixture was washed with water and sat. NaCl solution, dried over sodium sulfate and concentrated under reduced pressure. The crude product was purified by column chromatography. Yield: 43%

Workup

  1. customthe reaction mixture was degassed under argon for 20 minutes
  2. temperatureheated
  3. temperatureunder reflux for 4 h
  4. additionThe mixture was then diluted with ethyl acetate
  5. filtrationfiltered over Celite
  6. washThe reaction mixture was washed with water and sat. NaCl solution
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customThe crude product was purified by column chromatography

Sources & evidence

ORD record
ord-3a6244f38b4940adbcd2b85956b1f419
Source dataset
uspto-grants-2013_06
Patent number
US08455475B2

Reaction notes

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