4-Vinylpyridine → 3-(1-Boc-2-(s)-pyrrolidinyl-methoxy)-5-(4-pyridinyl-ethenyl)pyridine

HRID 365875Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 365875
[C:1]([N:8]1[CH2:12][CH2:11][CH2:10][C@H:9]1[CH2:13][O:14][C:15]1[CH:16]=[N:17][CH:18]=[C:19](Br)[CH:20]=1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].[CH:22]([C:24]1[CH:29]=[CH:28][N:27]=[CH:26][CH:25]=1)=[CH2:23].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C([O-])(O)=O.[Na+]>C(#N)C.CCN(CC)CC.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:1]([N:8]1[CH2:12][CH2:11][CH2:10][C@H:9]1[CH2:13][O:14][C:15]1[CH:16]=[N:17][CH:18]=[C:19]([CH:23]=[CH:22][C:24]2[CH:29]=[CH:28][N:27]=[CH:26][CH:25]=2)[CH:20]=1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2]

Komponenten

8

Edukt 4

HCID 75024-VinylpyridineHCID 80271Tri-o-tolylphosphineHCID 516892Sodium BicarbonateHCID 15480235(S)-2-((5-Bromopyridin-3-yloxy)methyl)pyrrolidine-1-carboxylic acid tert-butyl ester

Produkt 1

HCID 540343103-(1-Boc-2-(s)-pyrrolidinyl-methoxy)-5-(4-pyridinyl-ethenyl)pyridineAusbeute 80 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 167845palladium(II) acetateKatalysatorHCID 6342AcetonitrileLösungsmittelHCID 8471TriethylamineLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

To a solution of 3-(1-BOC-2-(S)-pyrrolidinylmethoxy)-5-bromopyridine (300 mg, 0.84 mmol) in acetonitrile (10 mL) and NEt3 (1 mL) was added 4-vinylpyridine(0.15 mL, 1.34 mmol), palladium acetate (28 mg, 0.13 mmol) and tri-o-tolylphosphine (141 mg). The reaction mixture was heated in a sealed tube at 100° C. for 16 h. After cooling to room temperature, saturated NaHCO3 solution was added. The mixture was extracted with EtOAc (2X). The combined organic solvent was dried (MgSO4), concentrated and chromatographed (silica gel; hexane/EtOAc, 2:1 to 1:2) to afford an oil (255 mg, 80%): 1H NMR (CDCl3, 300 Hz) δ1.50 (s, 9H), 1.90 (m, 1H), 2.00-2.10 (m, 2H), 3.30-3.50 (m, 2H), 4.00 (m, 1H), 4.14-4.24 (m, 2H), 4.28 (m, 1H), 7.10 (m, 1H), 7.24 (m, 1H), 7.36-7.40 (m, 3H), 8.26 (s, 1H), 8.30 (s, 1H), 8.60 (d, 2H, J=6.5 Hz); MS (CI/NH3) m/z 382 (M+H)+.

Aufarbeitung

  1. temperatureAfter cooling to room temperature
  2. extractionThe mixture was extracted with EtOAc (2X)
  3. dry with materialThe combined organic solvent was dried (MgSO4)
  4. concentrationconcentrated
  5. customchromatographed (silica gel; hexane/EtOAc, 2:1 to 1:2)

Quellen und Nachweise

ORD-Eintrag
ord-84eb9f36a7014b589ea3914f8539a35d
Quelldatensatz
uspto-grants-2000_10
Patentnummer
US06127386

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