تفاعل #162415

معادلة التفاعل

tert-butyl pyridin-3-ylcarbamate

tert-butyllithium

1-piperidinecarboxaldehyde

→

desired product

المردود 60.3%

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

المردود 60.3%

المذيبات

THF

pentane

ظروف التفاعل

المعالجة

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

الإجراء التجريبي

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.

المصدر