반응 #742261

반응 방정식

magnesium

epothilone A

→

epothilone C

수율 80.0%

용매

THF

반응 조건

후처리

1. 1
   workup.ADDITIONTo a two-necked flask was added
2. 2
   기타The flask was flame-dried under vacuum
3. 3
   온도cooled under argon
4. 4
   기타The stirring suspension was evacuated with low vacuum
5. 5
   workup.ADDITIONthe reaction flask was refilled with argon
6. 6
   기타homogeneous deep green after 1.5 h
7. 7
   기타being consumed
8. 8
   기타An aliquot (3.5 mL, 0.70 mmol, 3.5 eq) was removed
9. 9
   온도The reaction mixture was warmed to room temperature
10. 10
    기타The volatiles were removed in vacuo
11. 11
    기타the residue was chromatographed two times on silica (25 g)
12. 12
    세척eluting with 35% EtOAc/hexanes

실험 절차

To a two-necked flask was added chopped pieces of magnesium turnings (24 mg, 1.0 mmol). The flask was flame-dried under vacuum and cooled under argon. Bis(cyclopentadienyl)titanium dichloride (250 mg, 1.0 mmol) was added followed by anhydrous THF (5 mL). The stirring suspension was evacuated with low vacuum, and the reaction flask was refilled with argon. The red suspension became dark, turning a homogeneous deep green after 1.5 h with nearly all the magnesium metal being consumed. An aliquot (3.5 mL, 0.70 mmol, 3.5 eq) was removed and cooled to −78° C. under argon. To this solution was added epothilone A (99 mg, 0.20 mmol, 1.0 eq). The reaction mixture was warmed to room temperature and stirred for 15 min. The volatiles were removed in vacuo and the residue was chromatographed two times on silica (25 g), eluting with 35% EtOAc/hexanes to give 76 mg (80%) of epothilone C as a pale yellow viscous oil.

출처