Sodium Carbonate → HCID 57756257, compound

HRID 593922Notes

Reaction equation

HRID 593922 reaction equation
I[C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[N:8](C(OC(C)(C)C)=O)[N:9]=[CH:10][C:3]=12.[Cl:18][C:19]1[C:24](B(O)O)=[CH:23][CH:22]=[CH:21][N:20]=1.C(=O)([O-])[O-].[Na+].[Na+].F[B-](F)(F)F.C([PH+](C(C)(C)C)C(C)(C)C)(C)(C)C>CCOC(C)=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O.O1CCOCC1>[Cl:18][C:19]1[C:24]([C:2]2[CH:7]=[CH:6][N:5]=[C:4]3[NH:8][N:9]=[CH:10][C:3]=23)=[CH:23][CH:22]=[CH:21][N:20]=1

Participants

9

Reactant 4

HCID 10340Sodium CarbonateHCID 2734635Tri-tert-butylphosphine tetrafluoroborateHCID 2762704(2-Chloropyridin-3-yl)boronic acidHCID 66731818tert-Butyl 4-iodo-1H-pyrazolo[3,4-b]pyridine-1-carboxylate

Product 1

HCID 57756257HCID 57756257, compound

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

To tert-butyl 4-iodo-1H-pyrazolo[3,4-b]pyridine-1-carboxylate (1.00 g, 2.90 mmol), 2-chloropyridin-3-ylboronic acid (1.14 g, 7.24 mmol), and sodium carbonate (1.23 g, 11.6 mmol) was added dioxane (10 mL) and water (4 mL). The mixture was stirred at RT for 5 minutes, then tri-t-butylphosphonium tetrafluoroborate (0.084 g, 0.290 mmol) and palladium(II) acetate (0.033 g, 0.145 mmol) were added and the mixture was heated to 100° C. in a sealed tube for 23 hours. The reaction was diluted with EtOAc and extracted with 1N sodium bicarbonate. The organics were dried over sodium sulfate, filtered and concentrated. The crude was purified by ISCO silica gel chromatography (10-90% EtOAc/hexanes; 80 g column) and product fractions were concentrated to yield 4-(2-chloropyridin-3-yl)-1H-pyrazolo[3,4-b]pyridine as a white solid. MS m/z=231 [M+1]+. Calc'd for C11H7ClN4: 230.66.

Workup

  1. temperaturethe mixture was heated to 100° C. in a sealed tube for 23 hours
  2. extractionextracted with 1N sodium bicarbonate
  3. dry with materialThe organics were dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe crude was purified by ISCO silica gel chromatography (10-90% EtOAc/hexanes; 80 g column) and product fractions
  7. concentrationwere concentrated

Sources & evidence

ORD record
ord-e73c36580a1b4bd0b44c99e967fb520e
Source dataset
uspto-grants-2016_01
Patent number
US09242961B2

Reaction notes

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