Реакция #742261

Уравнение реакции

magnesium

epothilone A

→

epothilone C

Выход 80.0%

Растворители

THF

Условия реакции

Обработка

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

Методика

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.

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