反応 #43408

反応方程式

1,1-dimethylethyl [2-chloro-5-fluoro-6-(methyloxy)-3-pyridinyl]carbamate

caesium fluoride

tributyl[1-(ethyloxy)ethenyl]stannane

potassium fluoride

→

1,1-Dimethylethyl [2-[1-(ethyloxy)ethenyl]-5-fluoro-6-(methyloxy)-3-pyridinyl]carbamate

溶媒

1,4-dioxane

反応条件

後処理

1. 1
   ろ過the mixture was filtered through Kieselguhr
2. 2
   洗浄washing with 1,4-dioxane
3. 3
   workup.ADDITIONEthyl acetate and water were added to the filtrate
4. 4
   その他The phases were separated
5. 5
   抽出the aqueous phase extracted twice with ethyl acetate
6. 6
   乾燥The combined organic extracts were dried over magnesium sulphate
7. 7
   その他evaporated
8. 8
   その他The residue was rapidly chromatographed
9. 9
   洗浄eluting with 25-50% dichloromethane in hexane affording the product as a light brown oil (22.2 g, 99%)

実験手順

A degassed solution of 1,1-dimethylethyl [2-chloro-5-fluoro-6-(methyloxy)-3-pyridinyl]carbamate (20 g, 72.2 mmol) in 1,4-dioxane (200 ml) was treated with bis(tri-tert-butylphosphine) palladium(0) (1.05 g), caesium fluoride (21.93 g) and tributyl[1-(ethyloxy)ethenyl]stannane (26.9 ml) then heated to 100° C. overnight. The cooled mixture was treated with 10% aqueous potassium fluoride solution. After 0.5 hour stirring, the mixture was filtered through Kieselguhr, washing with 1,4-dioxane. Ethyl acetate and water were added to the filtrate. The phases were separated and the aqueous phase extracted twice with ethyl acetate. The combined organic extracts were dried over magnesium sulphate and evaporated. The residue was rapidly chromatographed eluting with 25-50% dichloromethane in hexane affording the product as a light brown oil (22.2 g, 99%).

出典