tert-Butyl acrylate → (E)-7-(2-tert-Butoxycarbonyl-vinyl)-2-oxo-1,2,3,5-tetrahydro-pyrido[2,3-e][1,4]diazepine-4-carboxylic acid benzyl ester

HRID 1362092Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1362092
[CH2:1]([O:8][C:9]([N:11]1[CH2:17][C:16]2[CH:18]=[C:19](Br)[CH:20]=[N:21][C:15]=2[NH:14][C:13](=[O:23])[CH2:12]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:24]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])(=[O:27])[CH:25]=[CH2:26].C(N(C(C)C)C(C)C)C.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>C(#N)CC.CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH2:1]([O:8][C:9]([N:11]1[CH2:17][C:16]2[CH:18]=[C:19](/[CH:26]=[CH:25]/[C:24]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])[CH:20]=[N:21][C:15]=2[NH:14][C:13](=[O:23])[CH2:12]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Komponenten

8

Edukt 4

HCID 15458tert-Butyl acrylateHCID 80271Tri-o-tolylphosphineHCID 81531DiisopropylethylamineHCID 594569487-Bromo-2-oxo-1,2,3,5-tetrahydro-pyrido[2,3-e][1,4]diazepine-4-carboxylic acid benzyl ester

Produkt 1

HCID 59456961(E)-7-(2-tert-Butoxycarbonyl-vinyl)-2-oxo-1,2,3,5-tetrahydro-pyrido[2,3-e][1,4]diazepine-4-carboxylic acid benzyl esterAusbeute 53 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 167845palladium(II) acetateKatalysatorHCID 6228DimethylformamideLösungsmittelHCID 7854PropionitrileLösungsmittel

Versuchsvorschrift

A suspension of 7-bromo-2-oxo-1,2,3,5-tetrahydro-pyrido[2,3-e][1,4]diazepine-4-carboxylic acid benzyl ester (0.52 g, 1.4 mmol) in propionitrile (10 mL) and DMF (3 mL) was de-oxygenated with Ar for 20 min. The mixture was treated with tert-butyl acrylate (0.83 mL, 10 mmol) and (i-Pr)2EtN (0.50 mL, 2.9 mmol) and was de-oxygenated with Ar for 10 min. Pd(OAc)2 (34 mg, 0.15 mmol) and P(o-tol)3 (84 mg, 0.27 mmol) were added simultaneously, and the mixture was de-oxygenated a third time for 5 min. The mixture was heated to reflux overnight, then allowed to cool. The resulting precipitate was isolated by filtration, washed with EtOAc and dissolved in CH2Cl2. The solution was filtered through Celite and the solvent was removed in vacuo to give the title compound (0.31 g, 53%) as an off-white solid: 1H NMR (300 MHz, CDCl3) δ 8.49-8.57 (m, 1H), 8.30 (s, 1H), 7.43-7.73 (m, 2H), 7.33 (s, 4H), 7.17-7.18 (m, 1H), 6.21-6.40 (m, 1H), 5.05-5.11 (m, 2H), 4.46-4.68 (m, 4H), 1.54-1.57 (m, 9H); MS (ESI) m/e 424 (M+H)+.

Aufarbeitung

  1. waitwas de-oxygenated with Ar for 10 min
  2. customfor 5 min
  3. temperatureThe mixture was heated
  4. temperatureto reflux overnight
  5. temperatureto cool
  6. customThe resulting precipitate was isolated by filtration
  7. washwashed with EtOAc
  8. dissolutiondissolved in CH2Cl2
  9. filtrationThe solution was filtered through Celite
  10. customthe solvent was removed in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-03831e89ef4c421cbb40a9d686e10a71
Quelldatensatz
uspto-grants-2011_02
Patentnummer
US07879872B2

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