反应 #1465

ord-833ae973b3214608bac2a8fbd227ff25

反应方程式

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

反应条件

温度
-78°CELSIUS
详细条件
See reaction.notes.procedure_details.

后处理

  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
    其他The reaction was quenched by the addition of sat. aqueous NH4Cl
  5. 5
    萃取The mixture was extracted with EtOAc (2×)
  6. 6
    洗涤washed with brine
  7. 7
    干燥The organic phase was dried over Na2SO4
  8. 8
    浓缩concentrated in vacuo
  9. 9
    其他The crude material product was purified by flash chromatography (silica, 15% ethyl acetate in hexanes)

实验过程

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.

来源

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