反応 #1465

ord-833ae973b3214608bac2a8fbd227ff25

反応方程式

CCOC(=O)c1ccc(/C=C/c2ccc3c(c2)C(OS(=O)(=O)C(F)(F)F)=CCC3(C)C)cc1
ethyl(E)-4-[2-(5,5-dimethyl-8-(trifluoromethylsulfonyl)oxy-5,6-dihydronaphthalen-2-yl)ethenyl]benzoate
CCOC(=O)c1ccc(/C=C/c2ccc3c(c2)C(OS(=O)(=O)C(F)(F)F)=CCC3(C)C)cc1
ethyl (E)-4-[2-(5,5-dimethyl-8-(trifluoromethylsulfonyl)oxy-5,6-dihydronaphthalen-2-yl)ethenyl]benzoate
CCOC(=O)c1ccc(/C=C/c2ccc3c(c2)C(OS(=O)(=O)C(F)(F)F)=CCC3(C)C)cc1
Compound A9
CCOC(=O)c1ccc(/C=C/c2ccc3c(c2)C(OS(=O)(=O)C(F)(F)F)=CCC3(C)C)cc1
ethyl (E)-4-[2-(5,5-dimethyl-8-(trifluoromethylsulfonyl)oxy-5,6-dihydronaphthalen-2-yl)ethenyl]benzoate
c1ccsc1
thiophene
[Li][CH2]CCC
n-butyl lithium
[Li][c]1cccs1
lithiothiophene
CCOC(=O)c1ccc(/C=C/c2ccc3c(c2)C(c2cccs2)=CCC3(C)C)cc1
title compound
CCOC(=O)c1ccc(/C=C/c2ccc3c(c2)C(c2cccs2)=CCC3(C)C)cc1
Ethyl (E)-4-[2-(-5,5-dimethyl-8-(2-thienyl)-5,6-dihydronaphthalen-2-yl)ethenyl]-benzoate

反応条件

温度
-78°CELSIUS
詳細条件
See reaction.notes.procedure_details.

後処理

  1. 1
    workup.STIRRINGThe resulting solution was stirred at -78° C. to room temperature for 1 h
  2. 2
    workup.STIRRINGThe resulting mixture was stirred at room temperature for 10 min
  3. 3
    温度heated at 50° C. for 1 h
  4. 4
    その他The reaction was quenched by the addition of sat. aqueous NH4Cl
  5. 5
    抽出The mixture was extracted with EtOAc (2×)
  6. 6
    洗浄washed with brine
  7. 7
    乾燥The organic phase was dried over Na2SO4
  8. 8
    濃縮concentrated in vacuo
  9. 9
    その他The crude material product was purified by flash chromatography (silica, 15% ethyl acetate in hexanes)

実験手順

A solution of lithiothiophene was prepared by the addition of 0.10 g (0.095 mL, 1.2 mmol) of thiophene to a cold solution (-78° C.) of 0.61 g (0.90 mL, 1.4 mmol, 1.6M in hexanes) of n-butyl lithium in 2.0 mL of tetrahydrofuran. The solution was stirred at -78° C. for 35 min and then a solution of 0.158 g (1.2 mmol) of zinc chloride in 2.0 mL of tetrahydrofuran was added. The resulting solution was stirred at -78° C. to room temperature for 1 h and then the organozinc was added via cannula to a mixture of 0.212 g (0.44 mmol) of ethyl(E)-4-[2-(5,5-dimethyl-8-(trifluoromethylsulfonyl)oxy-5,6-dihydronaphthalen-2-yl)ethenyl]benzoate (Compound A9) and 18 mg (0.016 mmol) of tetrakis(triphenylphosphine)palladium(0) in 2.0 mL of tetrahydrofuran. The resulting mixture was stirred at room temperature for 10 min and then heated at 50° C. for 1 h. The reaction was quenched by the addition of sat. aqueous NH4Cl. The mixture was extracted with EtOAc (2×), and washed with brine. The organic phase was dried over Na2SO4 and then concentrated in vacuo. The crude material product was purified by flash chromatography (silica, 15% ethyl acetate in hexanes) to afford the title compound as a solid.

出典

DOI: 10.6084/m9.figshare.5104873.v1特許: US05723666uspto-grants-1998_03