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

HRID 525995ノート

反応式

HRID 525995 の反応式
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]

参加物

7

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 3

HCID 23938Palladium触媒HCID 15220664Palladium--triphenylphosphane (1/1)触媒HCID 1140Toluene溶媒

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-06549fbd826b44eea2e0a24b88ab1f05
出典データセット
uspto-grants-2016_05
特許番号
US09345244B2

反応ノート

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