Cesium carbonate → 5,6'-Dimethyl-2,2'-bipyridin-4-amine

HRID 1522557Notes

Reaction equation

HRID 1522557 reaction equation
C(=O)([O-])[O-].[Cs+].[Cs+].Br[C:8]1[CH:13]=[C:12]([NH2:14])[C:11]([CH3:15])=[CH:10][N:9]=1.[CH3:16][C:17]1[N:22]=[C:21](B2OCCN(C3C=CC=CC=3)CCO2)[CH:20]=[CH:19][CH:18]=1>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].[Cu]Cl>[CH3:15][C:11]1[C:12]([NH2:14])=[CH:13][C:8]([C:21]2[CH:20]=[CH:19][CH:18]=[C:17]([CH3:16])[N:22]=2)=[N:9][CH:10]=1

Participants

8

Reactant 3

HCID 10796Cesium carbonateHCID 126437092-Bromo-5-methylpyridin-4-amineHCID 162178586-Methylpyridine-2-boronic acid N-phenyldiethanolamine ester

Product 1

HCID 674695755,6'-Dimethyl-2,2'-bipyridin-4-amineYield 21.7%

Reagents, catalysts & solvents 4

HCID 62652Cuprous chlorideCatalystHCID 167845palladium(II) acetateCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
105 °C

Procedure

Cesium carbonate (331 mg, 1.017 mmol), palladium acetate (5.71 mg, 0.025 mmol), 1,1′-bis(diphenylphosphino)ferrocene (28.5 mg, 0.051 mmol), copper(I)chloride (50.4 mg, 0.509 mmol), 2-bromo-5-methylpyridin-4-amine (200 mg, 1.069 mmol) and 2-(6-methylpyridin-2-yl)-6-phenyl-1,3,6,2-dioxazaborocane (287 mg, 1.017 mmol) were combined in DMF (5 mL) and heated at 105° C. for 2 days. The reaction mixture was then cooled and evaporated on a rotovap to give a residue which was purified by preparative HPLC eluting with a gradient of 5-30% acetonitrile (containing 0.035% TFA) in water (containing 0.05% TFA) using a Sunfire Prep 5 μm C18, 30×75 mm column to afford the title compound as a yellow crystalline solid (44 mg). ESI-MS: m/z 200.2 (M+H).

Workup

  1. temperatureThe reaction mixture was then cooled
  2. customevaporated on a rotovap
  3. customto give a residue which
  4. customwas purified by preparative HPLC
  5. washeluting with a gradient of 5-30% acetonitrile (containing 0.035% TFA) in water (containing 0.05% TFA)

Sources & evidence

ORD record
ord-249b88e4ddc0431aabe8606533998645
Source dataset
uspto-grants-2015_07
Patent number
US09073918B2

Reaction notes

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