Реакция #43408

Уравнение реакции

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

Растворители

1,4-dioxane

Условия реакции

Обработка

1. 1
   Фильтрацияthe mixture was filtered through Kieselguhr
2. 2
   Промывкаwashing with 1,4-dioxane
3. 3
   workup.ADDITIONEthyl acetate and water were added to the filtrate
4. 4
   ДругоеThe phases were separated
5. 5
   Экстракцияthe aqueous phase extracted twice with ethyl acetate
6. 6
   СушкаThe combined organic extracts were dried over magnesium sulphate
7. 7
   Другоеevaporated
8. 8
   ДругоеThe residue was rapidly chromatographed
9. 9
   Промывкаeluting with 25-50% dichloromethane in hexane affording the product as a light brown oil (22.2 g, 99%)

Методика

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%).

Источник