반응 #162415

반응 방정식

tert-butyl pyridin-3-ylcarbamate

tert-butyllithium

1-piperidinecarboxaldehyde

→

desired product

수율 60.3%

tert-butyl (4-formylpyridin-3-yl)carbamate

수율 60.3%

용매

THF

pentane

반응 조건

후처리

1. 1
   workup.ADDITIONUpon completion of the addition
2. 2
   workup.WAITat −20° C. for 1.5 h
3. 3
   온도was maintained below at −15° C.
4. 4
   workup.STIRRINGto stir at room temperature overnight
5. 5
   온도The solution was cooled to 0° C.
6. 6
   기타was quenched by the addition of 1 M HCl
7. 7
   workup.ADDITIONSolid Na2CO3 was then added
8. 8
   추출The solution was extracted with ethyl acetate three times
9. 9
   세척the combined organic solutions were washed with water (3×) and brine
10. 10
    기타The organic layer was dried
11. 11
    여과filtered
12. 12
    기타volatiles evaporated
13. 13
    기타The residue was purified by silica gel chromatography (50% ethyl acetate/hexanes)

실험 절차

A solution of tert-butyl pyridin-3-ylcarbamate (17.7 g, 91.1 mmol) in THF (300 mL) was cooled to −78° C. and treated with 1.70 M tert-butyllithium in pentane (129 mL). Upon completion of the addition, the reaction was stirred at −78° C. for an additional 15 min and then at −20° C. for 1.5 h. 1-piperidinecarboxaldehyde (30.4 mL, 0.273 mol) was added while the temperature was maintained below at −15° C., and then the mixture was allowed to stir at room temperature overnight. The solution was cooled to 0° C. and was quenched by the addition of 1 M HCl to bring the pH to 2. Solid Na2CO3 was then added to adjust the pH to 7. The solution was extracted with ethyl acetate three times, and the combined organic solutions were washed with water (3×) and brine. The organic layer was dried, filtered, and volatiles evaporated. The residue was purified by silica gel chromatography (50% ethyl acetate/hexanes) to give the desired product as a yellow solid (12.2 g, 60%). LCMS for C11H15N2O3(M+H)+: m/z=223.1.

출처