Bromobenzene → Methyl 5-oxo-1-phenylprolinate

HRID 534824

Reaktionsgleichung

Reaktionsgleichung von HRID 534824
[CH3:1][O:2][C:3]([CH:5]1[CH2:9][CH2:8][C:7](=[O:10])[NH:6]1)=[O:4].Br[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.C(=O)([O-])[O-]>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[O:10]=[C:7]1[N:6]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C@H:5]([C:3]([O:2][CH3:1])=[O:4])[CH2:9][CH2:8]1

Komponenten

7

Edukt 4

HCID 7961BromobenzeneHCID 19660Carbonate IonHCID 500249Methyl 5-oxo-DL-prolinateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)

Produkt 1

HCID 42260998Methyl 5-oxo-1-phenylprolinateAusbeute 49 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
120 °C

Versuchsvorschrift

A mixture of 5-oxo-pyrrolidine-2-carboxylic acid methyl ester (5.00 g, 34.9 mmol), bromobenzene (5.48 g, 34.9 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.96 g, 1.05 mmol), Xantphos™ (1.21 g, 2.09 mmol), and cecium carbonate (15.9 g, 48.9 mmol) in toluene (100 mL) was stirred at 120° C. for 20 h under argon atmosphere. The reaction mixture was cooled to room temperature, and partitioned between ethyl acetate and 2 M HCl solution. The organic layer was washed with saturated NaHCO3 solution, and brine, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate 70:30 to 0:100) to give a yellow solid. The solid was triturated with hexane-diisopropyl ether to give the title compound (3.74 g, 49%) as a yellow solid.

Aufarbeitung

  1. temperatureThe reaction mixture was cooled to room temperature
  2. custompartitioned between ethyl acetate and 2 M HCl solution
  3. washThe organic layer was washed with saturated NaHCO3 solution, and brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate 70:30 to 0:100)
  8. customto give a yellow solid
  9. customThe solid was triturated with hexane-diisopropyl ether

Quellen und Nachweise

ORD-Eintrag
ord-dd26cb1e18be4408962ef6b7a9724af2
Quelldatensatz
uspto-grants-2014_10
Patentnummer
US08853215B2

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