Cesium carbonate → Methyl 6-isopropenyl-5'-methyl-2,2'-bipyridine-4-carboxylate

HRID 1909139Notes

Reaction equation

HRID 1909139 reaction equation
Cl[C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([C:12]([CH3:14])=[CH2:13])[N:11]=1)[C:5]([O:7][CH3:8])=[O:6].[CH3:15][C:16]1[CH:17]=[CH:18][C:19](B2OC(C)(C)C(C)(C)O2)=[N:20][CH:21]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1C=CC([PH+]([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.C1C=CC([PH+]([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.C(Cl)Cl.Cl[Pd]Cl.[Fe].[Cu]Cl>[C:12]([C:10]1[N:11]=[C:2]([C:19]2[CH:18]=[CH:17][C:16]([CH3:15])=[CH:21][N:20]=2)[CH:3]=[C:4]([C:5]([O:7][CH3:8])=[O:6])[CH:9]=1)([CH3:14])=[CH2:13]

Participants

8

Reactant 3

HCID 10796Cesium carbonateHCID 426145875-Methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridineHCID 86657035HCID 86657035, compound

Product 1

HCID 67337802Methyl 6-isopropenyl-5'-methyl-2,2'-bipyridine-4-carboxylateYield 86.9%

Reagents, catalysts & solvents 4

HCID 62652Cuprous chlorideCatalystHCID 167845palladium(II) acetateCatalystHCID 53485975CID 53485975CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of methyl 2-chloro-6-isopropenylisonicotinate (0.5 g, 2.36 mmol) in DMF (12 mL) were added 5-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (1.3 g, 5.9 mmol), palladium(II)acetate (26.5 mg, 0.12 mmol), cesium carbonate (1.54 g, 4.72 mmol), dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (0.13 g, 0.24 mmol) and copper(I) chloride (0.23 g, 2.36 mmol). The mixture was purged with argon and heated to 100° C. After 45 min, saturated aqueous NaHCO3 was added. The mixture was extracted with ethyl acetate (3×). The combined organic extracts were washed with water (3×), brine, dried over sodium sulfate, filtered and concentrated. Purification by silica gel chromatography (100% hexanes→75% hexanes/ethyl acetate) gave the title compound (0.55 g). MS 269.1 (M+1).

Workup

  1. customThe mixture was purged with argon
  2. additionsaturated aqueous NaHCO3 was added
  3. extractionThe mixture was extracted with ethyl acetate (3×)
  4. washThe combined organic extracts were washed with water (3×), brine
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customPurification by silica gel chromatography (100% hexanes→75% hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-35447c618dda4b00ad772e36627a22b5
Source dataset
uspto-grants-2013_12
Patent number
US08598209B2

Reaction notes

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