Triphenylphosphine → Methyl 4-oxo-4-[(5-vinyl-2-pyridyl)amino]butanoate

HRID 525995Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 525995
Br[C:2]1[CH:3]=[CH:4][C:5]([NH:8][C:9](=[O:16])[CH2:10][CH2:11][C:12]([O:14][CH3:15])=[O:13])=[N:6][CH:7]=1.[C:17]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C[CH:18]=1.C([Sn](CCCC)(CCCC)C=C)CCC>C1(C)C=CC=CC=1.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd]>[O:16]=[C:9]([NH:8][C:5]1[CH:4]=[CH:3][C:2]([CH:17]=[CH2:18])=[CH:7][N:6]=1)[CH2:10][CH2:11][C:12]([O:14][CH3:15])=[O:13]

Komponenten

7

Edukt 3

HCID 11776TriphenylphosphineHCID 81998TributylvinyltinHCID 1506825Methyl 4-[(5-bromopyridin-2-yl)amino]-4-oxobutanoate

Produkt 1

HCID 89443936Methyl 4-oxo-4-[(5-vinyl-2-pyridyl)amino]butanoateAusbeute 15 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 23938PalladiumKatalysatorHCID 15220664Palladium--triphenylphosphane (1/1)KatalysatorHCID 1140TolueneLösungsmittel

Versuchsvorschrift

To a solution of methyl 4-[(5-bromo-2-pyridyl)amino]-4-oxo-butanoate (commercially available: 0.25 g, 0.871 mmol) in toluene (10 mL) was added palladium; triphenylphosphane (0.101 g, 0.0871 mmol) and tributyl(vinyl)stannane (0.33 g, 0.30 mL, 1.04 mmol). The reaction mixture was refluxed overnight. Then, 0.05 eq of palladium triphenylphosphane and 0.6 eq of tritutylvinylstannane were added. Volatiles were removed under vacuum and residue taken up in acetonitrile. The acetonitrile phase was washed twice with hexane and concentrated under vacuum. The residue was purified by flash chromatography eluting with cyclohexane-ethyl acetate (3/1) to give methyl 4-oxo-4-[(5-vinyl-2-pyridyl)amino]butanoate (compound A40) (0.20 g, 15%). 1H NMR (400 MHz, CDCl3) 8.26 (s, 1H), 8.19 (sb, 1H), 8.15 (m, 2H), 7.76 (m, 1H), 6.65 (m, 1H), 5.34 (d, 1H), 5.30 (d, 1H), 3.72 (s, 3H), 2.75 (m, 4H) ppm.

Aufarbeitung

  1. temperatureThe reaction mixture was refluxed overnight
  2. customVolatiles were removed under vacuum and residue
  3. washThe acetonitrile phase was washed twice with hexane
  4. concentrationconcentrated under vacuum
  5. customThe residue was purified by flash chromatography
  6. washeluting with cyclohexane-ethyl acetate (3/1)

Quellen und Nachweise

ORD-Eintrag
ord-06549fbd826b44eea2e0a24b88ab1f05
Quelldatensatz
uspto-grants-2016_05
Patentnummer
US09345244B2

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