2,2'-Bipyridine → HCID 89467172, compound

HRID 1522522Notes

Reaction equation

HRID 1522522 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([C:12]([O:14][CH3:15])=[O:13])[C:5]2[C:10]([CH3:11])=[N:9][NH:8][C:6]=2[N:7]=1.[CH:16]1(B(O)O)[CH2:18][CH2:17]1.C(=O)([O-])[O-].[Na+].[Na+].N1C=CC=CC=1C1C=CC=CN=1.[NH4+].[Cl-]>ClCCCl.C([O-])(=O)C.[Cu+2].C([O-])(=O)C>[Cl:1][C:2]1[CH:3]=[C:4]([C:12]([O:14][CH3:15])=[O:13])[C:5]2[C:10]([CH3:11])=[N:9][N:8]([CH:16]3[CH2:18][CH2:17]3)[C:6]=2[N:7]=1

Participants

8

Reactant 5

HCID 14742,2'-Bipyridine2×HCID 10340Sodium Carbonate2×HCID 25517Ammonium ChlorideHCID 2760897Cyclopropylboronic acid2×HCID 178498049HCID 178498049, compound

Product 1

HCID 89467172HCID 89467172, compound

Reagents, catalysts & solvents 2

HCID 8895Cupric acetateCatalyst2×HCID 111,2-DichloroethaneSolvent3×

Conditions

Temperature
70 °C

Procedure

To a suspension of methyl 6-chloro-3-methyl-1H-pyrazolo[3,4-b]pyridine-4-carboxylate (510 mg, 2.260 mmol), cyclopropylboronic acid (388 mg, 4.52 mmol), sodium carbonate (479 mg, 4.52 mmol) in 1,2-Dichloroethane (DCE) (150 mL) was added a suspension of copper(II) acetate (411 mg, 2.260 mmol), 2,2′-bipyridine (353 mg, 2.260 mmol) in hot 1,2-dichloroethane. The contents were heated at 70° C. for 16 hours. Added cyclopropylboronic acid (388 mg, 4.52 mmol), sodium carbonate (479 mg, 4.52 mmol) followed by copper(II) acetate (411 mg, 2.260 mmol), 2,2′-bipyridine (353 mg, 2.260 mmol) in hot 1,2-dichloroethane and heated at 70° C. for 16 hours. The contents were cooled to room temperature followed by addition of 100 mL of saturated NH4Cl solution and the phases were separated. The aqueous layer was extracted with DCM twice. The combined organic layers were washed with brine, dried over MgSO4, filtered, and concentrated in vacuo. The crude residue was purified via silica gel chromatography (eluent: 0% to 20% gradient EtOAc:Hex). The product was collected as 310 mg. 1H NMR (400 MHz, DMSO-d6) δ ppm 0.95-1.26 (m, 4 H), 2.53 (s, 3 H), 3.75-3.91 (m, 1 H), 3.96 (s, 3 H), 7.55 (s, 1 H). LCMS(ES) [M+H]+266.0

Workup

  1. additionwas added
  2. temperatureheated at 70° C. for 16 hours
  3. temperatureThe contents were cooled to room temperature
  4. customthe phases were separated
  5. extractionThe aqueous layer was extracted with DCM twice
  6. washThe combined organic layers were washed with brine
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customThe crude residue was purified via silica gel chromatography (eluent: 0% to 20% gradient EtOAc:Hex)
  11. customThe product was collected as 310 mg

Sources & evidence

ORD record
ord-943a167deb424aa6b7cc05ec59faff62
Source dataset
uspto-grants-2015_07
Patent number
US09073924B2

Reaction notes

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