3-Bromopyridine hydrochloride → HCID 67547809, compound

HRID 1253756Notes

Reaction equation

HRID 1253756 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].Cl.Br[C:67]1[CH:68]=[N:69][CH:70]=[CH:71][CH:72]=1>C1(C)C=CC=CC=1.CC([O-])=O.CC([O-])=O.[Pd+2]>[C:47]([O:51][C:52]([N:54]1[CH2:59][CH2:58][C:57]2([CH2:64][CH2:63][N:62]([C:67]3[CH:68]=[N:69][CH:70]=[CH:71][CH:72]=3)[CH2:61][CH2:60]2)[CH2:56][CH2:55]1)=[O:53])([CH3:50])([CH3:48])[CH3:49]

Participants

6

Reactant 3

HCID 5221743-Bromopyridine hydrochlorideHCID 634876Binap, (A+-)-HCID 15296367tert-Butyl 3,9-diazaspiro[5.5]undecane-3-carboxylate

Product 1

HCID 67547809HCID 67547809, compoundYield 31%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Procedure

BINAP (147 mg, 0.23 mmol) and Pd(OAc)2 (159 mg, 0.74 mmol) was added to a mixture of 3,9-diazaspiro[5.5]undecane-3-carboxylic acid tert-butyl ester (3 g, 11.81 mmol), 3-bromopyridine HCl (2.29 g, 11.81 mmol) and sodium tert-butylate (3.4 g, 35.45 mmol) in toluene and the reaction mixture was degassed under argon for 20 minutes and heated under reflux for 4 h. After cooling to room temperature, the mixture was 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: 31%

Workup

  1. customthe reaction mixture was degassed under argon for 20 minutes
  2. temperatureheated
  3. temperatureunder reflux for 4 h
  4. additionthe mixture was 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-2b9fafa9647340d2b43223fd9163f453
Source dataset
uspto-grants-2013_06
Patent number
US08455475B2

Reaction notes

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