Potassium Carbonate → 4-Cyclopropylpyridin-2-amine

HRID 2283480Notes

Reaction equation

HRID 2283480 reaction equation
Cl[C:2]1[CH:7]=[CH:6][N:5]=[C:4]([NH2:8])[CH:3]=1.[CH:9]1(B(O)O)[CH2:11][CH2:10]1.C(=O)([O-])[O-].[K+].[K+]>O1CCOCC1.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]>[CH:9]1([C:2]2[CH:7]=[CH:6][N:5]=[C:4]([NH2:8])[CH:3]=2)[CH2:11][CH2:10]1

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 5818662-Amino-4-chloropyridineHCID 2760897Cyclopropylboronic acid

Product 1

HCID 457879154-Cyclopropylpyridin-2-amine

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 4-chloropyridin-2-amine (2.6 g, 15 mmol), cyclopropylboronic acid (2.6 g, 30 mmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1.2 g, 1.5 mmol), and potassium carbonate (4.0 g, 30 mmol) in 1,4-dioxane (40 mL) and water (5 mL) was stirred at 80° C. for 15 hours. After allowing to cool to room temperature, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (petroleum ether:ethyl acetate=5:1) to give 4-cyclopropylpyridin-2-amine. MS ESI calcd. for C8H11N2 [M+H]+135, found 135. 1H NMR (400 MHz, CDCl3) δ 7.91 (d, J=6.0 Hz, 1H), 6.31-6.29 (m, 1H), 6.23-6.22 (m, 1H), 4.99 (s, 2H), 1.79-1.72 (m, 1H), 1.06-1.01 (m, 2H), 0.78-0.74 (m, 2H).

Workup

  1. temperatureto cool to room temperature
  2. filtrationthe reaction mixture was filtered
  3. concentrationthe filtrate was concentrated under reduced pressure
  4. customThe residue was purified by column chromatography on silica gel (petroleum ether:ethyl acetate=5:1)

Sources & evidence

ORD record
ord-039e45e916954ba99dd370ccf7456855
Source dataset
uspto-grants-2015_09
Patent number
US09145391B2

Reaction notes

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