Potassium Carbonate → 4-Methylene-6-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-2,3-dihydropyrano[3,2-b]pyridine

HRID 2279271Notes

Reaction equation

HRID 2279271 reaction equation
CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.C([O-])([O-])=O.[K+].[K+].[CH3:49][C:50]1[N:51]=[C:52]([C:55]2[CH:56]=[N:57][CH:58]=[CH:59][CH:60]=2)[S:53][CH:54]=1.Br[C:62]1[N:67]=[C:66]2[C:68](=[CH2:72])[CH2:69][CH2:70][O:71][C:65]2=[CH:64][CH:63]=1>C(OCC)(=O)C.O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:72]=[C:68]1[C:66]2=[N:67][C:62]([C:54]3[S:53][C:52]([C:55]4[CH:56]=[N:57][CH:58]=[CH:59][CH:60]=4)=[N:51][C:50]=3[CH3:49])=[CH:63][CH:64]=[C:65]2[O:71][CH2:70][CH2:69]1

Participants

8

Reactant 4

HCID 11430Potassium CarbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 12015543-(4-Methyl-1,3-thiazol-2-yl)pyridineHCID 584840716-bromo-4-methylene-3,4-dihydro-2H-pyrano[3,2-b]pyridine

Product 1

HCID 1317334814-Methylene-6-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-2,3-dihydropyrano[3,2-b]pyridineYield 22.1%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
120 °C

Procedure

To a stirred mixture of Pd2(dba)3 (270 mg, 0.3 mmol), xantphos (870 mg, 1.5 mmol), K2CO3 (1.52 g, 11 mmol) and 3-(4-methylthiazol-2-yl)pyridine (1.76 g, 10 mmol) in a sealed tube was added 6-bromo-4-methylene-2,3-dihydropyrano[3,2-b]pyridine (2.49 g, 11 mmol) in 1,4-dioxance (30 mL). The mixture was stirred at 120° C. for 18 hours. The mixture was diluted with Ethyl acetate and H2O, the organic layer was washed with brine and water, dried over Na2SO4, and concentrated in vacuo. The crude product was purified by silica gel chromatography (petroleum/Ethyl acetate=3/1) to give the title compound as red solid (710 mg, 22%). 1H NMR (400 Mz, DMSO-d6): δ: 2.69 (s, 3H); 2.81 (t, J=6, 2H); 4.25 (t, J=5.1, 2H); 5.16 (s, 1H); 6.16 (s, 1H); 7.38 (d, J=8.7, 1H); 7.55-7.50 (m, 1H); 7.6 (d, J=8.7, 1H); 8.31-8.27 (m, 1H); 8.66-8.64 (m, 1H); 9.12 (s, 1H).

Workup

  1. washthe organic layer was washed with brine and water
  2. dry with materialdried over Na2SO4
  3. concentrationconcentrated in vacuo
  4. customThe crude product was purified by silica gel chromatography (petroleum/Ethyl acetate=3/1)

Sources & evidence

ORD record
ord-50730b6847e4486a9d9e2adb71b172e4
Source dataset
uspto-grants-2015_09
Patent number
US09133218B2

Reaction notes

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