반응 #1771989

반응 방정식

triethylsilane

lithium triethylborohydride

tetrahydrofuran

triethylsilane

boron trifluoride

boron trifluoride

tert-butyl N-tert-butoxycarbonyl-4,4-dimethylpyroglutamate

tetrahydrofuran

→

Boc-Pro(4,4-dimethyl)-OtBu

tert-butyl N-tert-butoxycarbonyl-4,4-dimethylproline

반응 조건

후처리

1. 1
   기타the cooling bath was removed
2. 2
   workup.ADDITIONsaturated aqueous sodium bicarbonate (5 mL) was added
3. 3
   기타The reaction mixture was immersed in an ice/water bath
4. 4
   workup.ADDITION30% aqueous hydrogen peroxide (10 drops) was added
5. 5
   농축the reaction mixture was concentrated in vacuo
6. 6
   기타to remove the tetrahydrofuran
7. 7
   workup.ADDITIONThe aqueous solution was diluted with water (10 mL)
8. 8
   추출extracted with dichloromethane (3×40 mL)
9. 9
   건조The organic layers were dried (Na2SO4)
10. 10
    여과filtered
11. 11
    농축concentrated
12. 12
    workup.DISSOLUTIONThe residue was dissolved in dichloromethane (20 mL)
13. 13
    workup.STIRRINGStirring
14. 14
    workup.ADDITIONwere added
15. 15
    workup.STIRRINGAfter stirring at −78° C. for an additional two hours
16. 16
    기타the cooling bath was removed
17. 17
    workup.ADDITIONsaturated aqueous sodium bicarbonate (4 mL) was added
18. 18
    추출After 5 minutes the mixture was extracted with dichloromethane (3×40 mL)
19. 19
    건조The organic layers were dried (Na2SO4)
20. 20
    여과filtered
21. 21
    농축concentrated

실험 절차

To a solution of tert-butyl N-tert-butoxycarbonyl-4,4-dimethylpyroglutamate (2.0 mmol) in tetrahydrofuran (5 mL) stirring at −78° C., was added a 1M solution of lithium triethylborohydride in tetrahydrofuran (2.4 mL, 2.4 mmol) dropwise over 5 minutes. After 30 minutes, the cooling bath was removed and saturated aqueous sodium bicarbonate (5 mL) was added. The reaction mixture was immersed in an ice/water bath and 30% aqueous hydrogen peroxide (10 drops) was added. The solution was stirred for 20 minutes at 0° C., then the reaction mixture was concentrated in vacuo to remove the tetrahydrofuran. The aqueous solution was diluted with water (10 mL) and extracted with dichloromethane (3×40 mL). The organic layers were dried (Na2SO4), filtered and concentrated. The residue was dissolved in dichloromethane (20 mL) and triethylsilane (310 μL, 2.0 mmol), then cooled to −78° C. and boron trifluoride diethyletherate (270 μL, 2.13 mmol) was added dropwise. Stirring was continued for 30 minutes, at which time additional triethylsilane (310 μL, 2.0 mmol) and boron trifluoride diethyletherate (270 μL, 2.13 mmol) were added. After stirring at −78° C. for an additional two hours, the cooling bath was removed and saturated aqueous sodium bicarbonate (4 mL) was added. After 5 minutes the mixture was extracted with dichloromethane (3×40 mL). The organic layers were dried (Na2SO4), filtered and concentrated to give Boc-Pro(4,4-dimethyl)-OtBu.

출처