Cesium carbonate → tert-butyl 4-(4-(3-methyl-4-oxo-1-phenyl-4,7-dihydro-1H-pyrazolo[3,4-b]pyridin-6-yl)phenyl)piperazine-1-carboxylate

HRID 68737Notes

Reaction equation

HRID 68737 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[NH:13][C:12]3[N:14]([C:18]4[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=4)[N:15]=[C:16]([CH3:17])[C:11]=3[C:10](=[O:24])[CH:9]=2)=[CH:4][CH:3]=1.[N:25]1([C:31]([O:33][C:34]([CH3:37])([CH3:36])[CH3:35])=[O:32])[CH2:30][CH2:29][NH:28][CH2:27][CH2:26]1.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([O-])([O-])=O.[Cs+].[Cs+]>C1(C)C=CC=CC=1.CN(C=O)C.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].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2]>[CH3:17][C:16]1[C:11]2[C:10](=[O:24])[CH:9]=[C:8]([C:5]3[CH:6]=[CH:7][C:2]([N:28]4[CH2:27][CH2:26][N:25]([C:31]([O:33][C:34]([CH3:37])([CH3:36])[CH3:35])=[O:32])[CH2:30][CH2:29]4)=[CH:3][CH:4]=3)[NH:13][C:12]=2[N:14]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[N:15]=1

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 143452tert-Butyl piperazine-1-carboxylateHCID 634876Binap, (A+-)-HCID 1363862876-(4-bromophenyl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridin-4(7H)-one

Product 1

HCID 136386288tert-butyl 4-(4-(3-methyl-4-oxo-1-phenyl-4,7-dihydro-1H-pyrazolo[3,4-b]pyridin-6-yl)phenyl)piperazine-1-carboxylate

Reagents, catalysts & solvents 3

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 21735183Dimethylformamide tolueneSolvent

Conditions

Temperature
120 °C

Procedure

Into a 100 mL round-bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed a solution of 6-(4-bromophenyl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridin-4(7H)-one (2500 mg, 6.58 mmol, 1.00 equiv) in toluene/DMF (30 ml/1 ml mL), tert-butyl piperazine-1-carboxylate (6130 mg, 32.96 mmol, 5.00 equiv), BINAP (410 mg, 0.65 mmol, 0.10 equiv), Pd2(dba)3 (602.9 mg, 0.66 mmol, 0.10 equiv), Cs2CO3 (3819 mg, 19.79 mmol, 3.00 equiv), dppf (270 mg). The resulting solution was stirred overnight at 120° C. in an oil bath. The resulting mixture was concentrated under vacuum. The residue was applied onto a silica gel column with dichloromethane/methanol (1:10) to yield tert-butyl 4-(4-(3-methyl-4-oxo-1-phenyl-4,7-dihydro-1H-pyrazolo[3,4-b]pyridin-6-yl)phenyl)piperazine-1-carboxylate as a white solid.

Workup

  1. customInto a 100 mL round-bottom flask purged
  2. temperaturemaintained with an inert atmosphere of nitrogen
  3. concentrationThe resulting mixture was concentrated under vacuum

Sources & evidence

ORD record
ord-b98e8c06dc1d4e6186d03cf46e7a33e8
Source dataset
uspto-grants-2014_09
Patent number
US08822447B2

Reaction notes

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