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

HRID 460048

반응식

HRID 460048 반응식
[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]

참가 물질

9

반응물 5

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

생성물 1

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

시약·촉매·용매 3

HCID 3007855Zincchloride촉매HCID 9834912Nickel(II) acetylacetonate촉매HCID 8028Tetrahydrofuran용매3회

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온도
0 °C

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-0bc2aef8246b4881a449c43831cb7ec6
출처 데이터셋
uspto-grants-2007_03
특허 번호
US07196089B2

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