Ethyl bromoacetate → (5-Methyl-4-triisopropylsilanyloxymethyl-furan-2-yl)-acetic acid ethyl ester

HRID 490343

Reaktionsgleichung

Reaktionsgleichung von HRID 490343
[CH:1]([Si:4]([CH:16]([CH3:18])[CH3:17])([CH:13]([CH3:15])[CH3:14])[O:5][CH2:6][C:7]1[CH:11]=[CH:10][O:9][C:8]=1[CH3:12])([CH3:3])[CH3:2].C([Li])CCC.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Br[CH2:44][C:45]([O:47][CH2:48][CH3:49])=[O:46].[Cl-].O1C=CC=C1[Zn+]>O1CCCC1.[Cl-].[Zn+2].[Cl-].C/C(/[O-])=C/C(C)=O.C/C(/[O-])=C/C(C)=O.[Ni+2]>[CH2:48]([O:47][C:45](=[O:46])[CH2:44][C:10]1[O:9][C:8]([CH3:12])=[C:7]([CH2:6][O:5][Si:4]([CH:1]([CH3:3])[CH3:2])([CH:13]([CH3:15])[CH3:14])[CH:16]([CH3:18])[CH3:17])[CH:11]=1)[CH3:49]

Komponenten

9

Edukt 5

HCID 7748Ethyl bromoacetateHCID 11776TriphenylphosphineHCID 11043781Silane, tris(1-methylethyl)[(2-methyl-3-furanyl)methoxy]-HCID 178418339ButyllithiumHCID 178479832HCID 178479832, Verbindung

Produkt 1

HCID 58824185(5-Methyl-4-triisopropylsilanyloxymethyl-furan-2-yl)-acetic acid ethyl ester

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 3007855ZincchlorideKatalysatorHCID 9834912Nickel(II) acetylacetonateKatalysatorHCID 8028TetrahydrofuranLösungsmittel3×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

A solution of triisopropyl-(2-methyl-furan-3-ylmethoxy)-silane (14) (5.0 g) in tetrahydrofuran (15 mL) was cooled to −78° C. with stirring. This solution was treated drop-wise with n-butyl lithium (2.5 M in hexanes, 8.94 mL). The resulting solution was warmed to 0° C. and allowed to stand for 30 minutes after which a solution of dried zinc chloride (3.04 g) in tetrahydrofuran (10 mL) was added and the resulting solution allowed to stand for a further 1 hour at room temperature. Concurrently, a second reaction vessel was charged with tetrahydrofuran (10 mL), nickel(II) acetylacetonate (120 mg), and triphenylphosphine (122 mg) and cooled (−5° C.). Ethyl bromoacetate (1.03 mL) was added to this mixture, followed by the addition of the previously prepared solution of the furyl-zinc chloride. The resulting reaction mixture was allowed to warm to room temperature then stirred for a further 16 hours at room temperature. The reaction was quenched by the addition of saturated ammonium chloride solution (100 mL) and extracted with ethyl acetate (3×150 mL). The combined organic extracts were successively washed with water (200 mL) and brine (250 mL), dried, filtered and concentrated in vacuo. The residue was purified by flash chromatography using a gradient elution (diethyl ether/petroleum ether (40-60°) 1:49 to 1:25 by volume) to give compound 29 as a clear oil (1.44 g). LC/MS System A: Rt=5.16 min.

Aufarbeitung

  1. waitto stand for a further 1 hour at room temperature
  2. temperaturecooled (−5° C.)
  3. customThe resulting reaction mixture
  4. temperatureto warm to room temperature
  5. stirringthen stirred for a further 16 hours at room temperature
  6. customThe reaction was quenched by the addition of saturated ammonium chloride solution (100 mL)
  7. extractionextracted with ethyl acetate (3×150 mL)
  8. washThe combined organic extracts were successively washed with water (200 mL) and brine (250 mL)
  9. customdried
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customThe residue was purified by flash chromatography
  13. washa gradient elution (diethyl ether/petroleum ether (40-60°) 1:49 to 1:25 by volume)

Quellen und Nachweise

ORD-Eintrag
ord-787570d1d6d748748887de43d759e0c5
Quelldatensatz
uspto-grants-2009_05
Patentnummer
US07528157B2

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