Tri-o-tolylphosphine → HCID 54009539, Verbindung

HRID 2305113Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2305113
Br[C:2]1[CH:3]=[C:4]([O:9][CH2:10][C@H:11]2[CH2:15][CH2:14][CH2:13][N:12]2[C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH:5]=[N:6][C:7]=1Cl.[CH3:23][C:24]([CH3:30])([CH3:29])[CH:25]=[CH:26][CH:27]=[CH2:28].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(=O)(O)[O-].[Na+]>C(#N)C.C(N(CC)CC)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:23][C:24]([CH3:30])([CH3:29])[CH:25]=[CH:26][CH:27]=[CH:28][C:2]1[CH:3]=[C:4]([O:9][CH2:10][C@H:11]2[CH2:15][CH2:14][CH2:13][N:12]2[C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH:5]=[N:6][CH:7]=1

Komponenten

8

Edukt 4

HCID 80271Tri-o-tolylphosphineHCID 1420695,5-Dimethyl-1,3-hexadieneHCID 516892Sodium BicarbonateHCID 22872666HCID 22872666, Verbindung

Produkt 1

HCID 54009539HCID 54009539, VerbindungAusbeute 42 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 167845palladium(II) acetateKatalysatorHCID 6342AcetonitrileLösungsmittelHCID 8471TriethylamineLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

To a solution of 5-bromo-6-chloro-3-(1-BOC-2-(R)-pyrrolidinylmethoxy)pyridine (600 mg, 1.59 mmol) in acetonitrile (5.0 mL) and triethylamine (4.5 mL) was added 5,5-dimethyl-1,3-hexadiene (228 mg), palladium acetate (39 mg) and tri-o-tolylphosphine (205 mg). After being heated in a sealed tube at 100° C. overnight, the resulting mixture was cooled to room temperature. Minimum amount of saturated sodium bicarbonate was added to free the amine hydrochloride salt, and the mixture was extracted with EtOAc, dried (MgSO4), and concentrated. The residue was chromatographed on a silica gel column, eluting with EtOAc:hexane 1:3 to afford the title compound (126 mg, 42% yield). MS (CI/NH3) m/z 307 (M+H)+. 1H NMR (CDCl3, 300 MHz) δ: 1.42 (s, 9H), 1.55 (s, 9H), 2.24-2.42 (m, 2H), 3.88 (t, J=7.5, 2H), 4.13 (dd, J=3, 7.5, 1H), 4.29-4.41 (m, 1H), 5.97 (d, J=15, 1H), 6.22 (dd, J=9, 15, 1H), 6.67-6.78 (m, 2H), 7.45 (br s, 1H), 8.95 (d, J=3.0, 1H).

Aufarbeitung

  1. temperaturethe resulting mixture was cooled to room temperature
  2. extractionthe mixture was extracted with EtOAc
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated
  5. customThe residue was chromatographed on a silica gel column
  6. washeluting with EtOAc:hexane 1:3

Quellen und Nachweise

ORD-Eintrag
ord-92cdd5c762ad4ba79cc1e5f7b730e6e5
Quelldatensatz
uspto-grants-2002_08
Patentnummer
US06437138B1

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