Potassium Carbonate → 4-Methylene-6-[1-(3-pyridyl)pyrazol-4-yl]-2,3-dihydropyrano[3,2-b]pyridine

HRID 1478548Notes

Reaction equation

HRID 1478548 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C([O-])([O-])=O.[K+].[K+].CC1(C)C(C)(C)OB([C:34]2[CH:35]=[N:36][N:37]([C:39]3[CH:40]=[N:41][CH:42]=[CH:43][CH:44]=3)[CH:38]=2)O1.Br[C:47]1[N:52]=[C:51]2[C:53](=[CH2:57])[CH2:54][CH2:55][O:56][C:50]2=[CH:49][CH:48]=1>[N+](CCCC)(CCCC)(CCCC)CCCC.[Cl-].CN(C=O)C.[Pd](Cl)Cl.O.CCOC(C)=O>[CH2:57]=[C:53]1[C:51]2=[N:52][C:47]([C:34]3[CH:35]=[N:36][N:37]([C:39]4[CH:40]=[N:41][CH:42]=[CH:43][CH:44]=4)[CH:38]=3)=[CH:48][CH:49]=[C:50]2[O:56][CH2:55][CH2:54]1

Participants

10

Reactant 4

HCID 11430Potassium CarbonateHCID 11776TriphenylphosphineHCID 574162183-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazol-1-yl)pyridineHCID 584840716-bromo-4-methylene-3,4-dihydro-2H-pyrano[3,2-b]pyridine

Product 1

HCID 900430134-Methylene-6-[1-(3-pyridyl)pyrazol-4-yl]-2,3-dihydropyrano[3,2-b]pyridine

Reagents, catalysts & solvents 5

HCID 24290Palladium ChlorideCatalystHCID 70681Tetrabutylammonium ChlorideCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

137 mg (0.78 mmol) of palladium chloride, 948 mg (3.62 mmol) of triphenylphosphine, 356 mg (25.8 mmol) of K2CO3 and 3.54 g (11.89 mmol) of n-Bu4NCl in 30 ml of DMF were heated under 105° C. for 10 min under N2. 3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyrazol-1-yl]pyridine (3.5 g, 12.92 mmol) and 6-bromo-4-methylene-2,3-dihydropyrano[3,2-b]pyridine (3.2 g, 14.16 mmol) in DMF (20 ml) were added to the above solution and stirred overnight. EtOAc and water were added to the reaction mixture. The aqueous phase was extracted with EtOAc for 3 times, the combined organic phase was washed with water for 3 times, dried over Na2SO4, and concentrated in vacuum. The crude product was purified by silica gel chromatography (petroleum/EtOAc=1/1) to get the title compound as red solid.

Workup

  1. extractionThe aqueous phase was extracted with EtOAc for 3 times
  2. washthe combined organic phase was washed with water for 3 times
  3. dry with materialdried over Na2SO4
  4. concentrationconcentrated in vacuum
  5. customThe crude product was purified by silica gel chromatography (petroleum/EtOAc=1/1)

Sources & evidence

ORD record
ord-52828185a0c74abb8826b4998badf38e
Source dataset
uspto-grants-2016_08
Patent number
US09403845B2

Reaction notes

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