Cesium carbonate → tert-butyl 3-methoxy-1-(4-methoxybenzyl)-1H-pyrazolo[3,4-b]pyridin-5-ylcarbamate

HRID 1943890Notes

Reaction equation

HRID 1943890 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:10]([O:11][CH3:12])=[N:9][N:8]([CH2:13][C:14]3[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=3)[C:5]2=[N:6][CH:7]=1.[C:22](=[O:29])([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])[NH2:23].C([O-])([O-])=O.[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1>C1COCC1.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]>[CH3:12][O:11][C:10]1[C:4]2[C:5](=[N:6][CH:7]=[C:2]([NH:23][C:22](=[O:29])[O:24][C:25]([CH3:28])([CH3:27])[CH3:26])[CH:3]=2)[N:8]([CH2:13][C:14]2[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=2)[N:9]=1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 77922tert-Butyl carbamateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 670888295-bromo-3-methoxy-1-(4-methoxybenzyl)-1H-pyrazolo[3,4-b]pyridine

Product 1

HCID 67089104tert-butyl 3-methoxy-1-(4-methoxybenzyl)-1H-pyrazolo[3,4-b]pyridin-5-ylcarbamateYield 24.8%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8028TetrahydrofuranSolvent

Procedure

5-Bromo-3-methoxy-1-(4-methoxybenzyl)-1H-pyrazolo[3,4-b]pyridine (0.109 g, 0.313 mmol), tert-butyl carbamate (0.110 g, 0.939 mmol), Cs2CO3 (0.153 g, 0.470 mmol), Pd2 dba3*CHCl3 (0.0324 g, 0.0313 mmol) and 4,5-bis(diphenylphosphino)-9,9 dimethylxanthene (0.0362 g, 0.0626 mmol) were taken up in THF, degassed with argon for 15 minutes, and heated to reflux overnight. The solution was partitioned between water and EtOAc. The organic portion was washed with water (3×), brine, dried over Na2SO4 and concentrated to an oil which was purified by column chromatography (4:1 hexane/EtOAc) to give tert-butyl 3-methoxy-1-(4-methoxybenzyl)-1H-pyrazolo[3,4-b]pyridin-5-ylcarbamate (0.0298 g, 24.8%) as an oil.

Workup

  1. customdegassed with argon for 15 minutes
  2. temperatureheated
  3. temperatureto reflux overnight
  4. customThe solution was partitioned between water and EtOAc
  5. washThe organic portion was washed with water (3×), brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated to an oil which
  8. customwas purified by column chromatography (4:1 hexane/EtOAc)

Sources & evidence

ORD record
ord-4361c26ced224f75b46778539bcdbf7f
Source dataset
uspto-grants-2013_03
Patent number
US08394795B2

Reaction notes

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