Epothilone A → Epothilone C

HRID 1245659

反応式

HRID 1245659 の反応式
[Mg].[CH3:2][C:3]1[S:7][CH:6]=[C:5](/[CH:8]=[C:9](/[C@H:11]2[O:29][C:27](=[O:28])[CH2:26][C@H:25]([OH:30])[C:24]([CH3:32])([CH3:31])[C:22](=[O:23])[C@H:21]([CH3:33])[C@@H:20]([OH:34])[C@@H:19]([CH3:35])[CH2:18][CH2:17][CH2:16][C@H:14]3O[C@H:13]3[CH2:12]2)\[CH3:10])[N:4]=1>[Cl-].[Cl-].C1([Ti+2]C2C=CC=C2)C=CC=C1.C1COCC1>[CH3:2][C:3]1[S:7][CH:6]=[C:5](/[CH:8]=[C:9](/[C@H:11]2[O:29][C:27](=[O:28])[CH2:26][C@H:25]([OH:30])[C:24]([CH3:32])([CH3:31])[C:22](=[O:23])[C@H:21]([CH3:33])[C@@H:20]([OH:34])[C@@H:19]([CH3:35])[CH2:18][CH2:17][CH2:16][CH:14]=[CH:13][CH2:12]2)\[CH3:10])[N:4]=1

参加物

5

反応物 2

HCID 448799Epothilone AHCID 5462224Magnesium

生成物 1

HCID 9891226Epothilone C収率 80%

試薬・触媒・溶媒 2

HCID 178420582HCID 178420582、化合物触媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

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.

後処理

  1. additionTo a two-necked flask was added
  2. customThe flask was flame-dried under vacuum
  3. temperaturecooled under argon
  4. customThe stirring suspension was evacuated with low vacuum
  5. additionthe reaction flask was refilled with argon
  6. customhomogeneous deep green after 1.5 h
  7. custombeing consumed
  8. customAn aliquot (3.5 mL, 0.70 mmol, 3.5 eq) was removed
  9. temperatureThe reaction mixture was warmed to room temperature
  10. customThe volatiles were removed in vacuo
  11. customthe residue was chromatographed two times on silica (25 g)
  12. washeluting with 35% EtOAc/hexanes

出典と根拠

ORDレコード
ord-0c14bfc6aeef48d6bdecfcfe838e6f7e
出典データセット
uspto-grants-2006_10
特許番号
US07125899B2

関連ノート

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