Tetrahydrofuran → HCID 55285543, compound

HRID 1260459Notes

Reaction equation

HRID 1260459 reaction equation
Br[C:2]1[C:7]([NH2:8])=[C:6]([CH3:9])[CH:5]=[CH:4][N:3]=1.[CH:10]1([B-](F)(F)F)[CH2:12][CH2:11]1.[K+].C([O-])([O-])=O.[Cs+].[Cs+].C1COCC1>CCOC(C)=O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl.O>[CH:10]1([C:2]2[C:7]([NH2:8])=[C:6]([CH3:9])[CH:5]=[CH:4][N:3]=2)[CH2:12][CH2:11]1

Participants

8

Reactant 4

HCID 8028TetrahydrofuranHCID 10796Cesium carbonateHCID 144180472-Bromo-4-methylpyridin-3-amineHCID 23697338Potassium cyclopropyltrifluoroborate

Product 1

HCID 55285543HCID 55285543, compound

Reagents, catalysts & solvents 3

HCID 178418807HCID 178418807, compoundCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

Following a modified synthetic procedure reported in J. Org. Chem. 2003, 68, 5534, a mixture of 2-bromo-4-methylpyridin-3-amine (1.0 eq.), potassium cyclopropyltrifluoroborate (2.0 eq.), Cs2CO3 (3.0 eq.) and PdCl2(dppf)-CH2Cl2 adduct (0.1 eq.) in 10:1 solution THF:H2O (0.14M) was put in a 10-mL glass vial equipped with a small magnetic stirring bar. The reaction vessel was fitted with a rubber septum, was evacuated and back-filled with argon and sealed with an aluminum/Teflon crimp top. The reaction mixture was then heated for O/N at 80° C. After completion of the reaction, the vial was cooled to RT before it was opened. The reaction mixture was diluted with EtOAc and filtered on a pad of Solca Floc®200FCC. The crude product was purified by flash chromatography eluting with 10-100% EtOAc/petroleum ether affording the titled compound as brown oil. 1H-NMR (400 MHz, DMSO-d6, 300K) δ 7.55 (1H, d, J=4.7 Hz), 6.75 (1H, d, J=4.7 Hz), 4.89 (2H, br. s), 2.13-2.04 (4H, m), 0.85-0.68 (4H, m). MS (ES) C9H12N2 requires: 148, found: 149 (M+H)+.

Workup

  1. customequipped with a small magnetic stirring bar
  2. customThe reaction vessel was fitted with a rubber septum
  3. customwas evacuated
  4. additionback-filled with argon
  5. customsealed with an aluminum/Teflon crimp top
  6. customAfter completion of the reaction
  7. temperaturethe vial was cooled to RT before it
  8. filtrationfiltered on a pad of Solca Floc®200FCC
  9. customThe crude product was purified by flash chromatography
  10. washeluting with 10-100% EtOAc/petroleum ether affording the titled compound as brown oil

Sources & evidence

ORD record
ord-e57c52c65bdb46a3914e58f1e500f3b1
Source dataset
uspto-grants-2013_06
Patent number
US08470823B2

Reaction notes

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