Sodium Carbonate → (S)-tert-butyl 4-(5-(4-(4-fluorophenyl)-2-oxooxazolidin-3-yl)pyrazolo[1,5-a]pyrimidin-3-yl)benzoate

HRID 539073Notes

Reaction equation

HRID 539073 reaction equation
Br[C:2]1[CH:3]=[N:4][N:5]2[CH:10]=[CH:9][C:8]([N:11]3[C@@H:15]([C:16]4[CH:21]=[CH:20][C:19]([F:22])=[CH:18][CH:17]=4)[CH2:14][O:13][C:12]3=[O:23])=[N:7][C:6]=12.[C:24]([O:28][C:29]([C:31]1[CH:36]=[CH:35][C:34](B(O)O)=[CH:33][CH:32]=1)=[O:30])([CH3:27])([CH3:26])[CH3:25].C([O-])([O-])=O.[Na+].[Na+].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1>O1CCOCC1.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]>[F:22][C:19]1[CH:20]=[CH:21][C:16]([C@H:15]2[CH2:14][O:13][C:12](=[O:23])[N:11]2[C:8]2[CH:9]=[CH:10][N:5]3[N:4]=[CH:3][C:2]([C:34]4[CH:35]=[CH:36][C:31]([C:29]([O:28][C:24]([CH3:25])([CH3:26])[CH3:27])=[O:30])=[CH:32][CH:33]=4)=[C:6]3[N:7]=2)=[CH:17][CH:18]=1

Participants

7

Reactant 4

HCID 10340Sodium CarbonateHCID 2773301(4-((Tert-butoxy)carbonyl)phenyl)boronic acidHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 67034438(S)-3-(3-bromopyrazolo[1,5-a]pyrimidin-5-yl)-4-(4-fluorophenyl)oxazolidin-2-one

Product 1

HCID 67034794(S)-tert-butyl 4-(5-(4-(4-fluorophenyl)-2-oxooxazolidin-3-yl)pyrazolo[1,5-a]pyrimidin-3-yl)benzoateYield 59%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

To a sealed tube was added (S)-3-(3-bromopyrazolo[1,5-a]pyrimidin-5-yl)-4-(4-fluorophenyl)oxazolidin-2-one (Preparation A; 0.200 g, 0.530 mmol), 4-(tert-butoxycarbonyl)phenyl boronic acid (0.177 g, 0.795 mmol) and 2.0 M Na2CO3 (0.795 mL, 1.59 mmol) in dioxane (1 mL). The mixture was degassed by bubbling N2 through the solution. Pd2 dba3 (0.0486 g, 0.053 mmol), and dicyclohexyl(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphine (0.0253 g, 0.053 mmol) were added and the vessel was sealed under a N2 atmosphere. The mixture was heated at 90° C. for 18 hours. The reaction mixture was cooled to ambient temperature, filtered through glass fiber filter paper, concentrated and purified on silica gel (10-100% ether in DCM) giving (S)-tert-butyl 4-(5-(4-(4-fluorophenyl)-2-oxooxazolidin-3-yl)pyrazolo[1,5-a]pyrimidin-3-yl)benzoate (0.148 g, 59% yield).

Workup

  1. customPreparation A
  2. customThe mixture was degassed
  3. customby bubbling N2 through the solution
  4. customthe vessel was sealed under a N2 atmosphere
  5. temperatureThe reaction mixture was cooled to ambient temperature
  6. filtrationfiltered through glass fiber
  7. filtrationfilter paper
  8. concentrationconcentrated
  9. custompurified on silica gel (10-100% ether in DCM)

Sources & evidence

ORD record
ord-ba25f9944ec5439489347f25766bc110
Source dataset
uspto-grants-2014_10
Patent number
US08865726B2

Reaction notes

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