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

HRID 525995노트

반응식

HRID 525995 반응식
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]

참가 물질

7

반응물 3

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

생성물 1

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

시약·촉매·용매 3

HCID 23938Palladium촉매HCID 15220664Palladium--triphenylphosphane (1/1)촉매HCID 1140Toluene용매

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-06549fbd826b44eea2e0a24b88ab1f05
출처 데이터셋
uspto-grants-2016_05
특허 번호
US09345244B2

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