2-allyl-6,6-dimethylfulvene

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 2-allyl-6,6-dimethylfulvene
• 英文别名: 5-Propan-2-ylidene-2-prop-2-enylcyclopenta-1,3-diene；5-propan-2-ylidene-2-prop-2-enylcyclopenta-1,3-diene
• 化学式: C₁₁H₁₄
• 分子量: 146.232
• InChiKey: UGNRPPRLJXULHQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2-allyl-6,6-dimethylfulvene 、 甲基锂 以 四氢呋喃 、 乙醚 为溶剂， 以96%的产率得到lithium 1-allyl-3-tert-butylcyclopentadienide
  参考文献：
  名称：

  Ring-closing metathesis of sterically congested functionalized zirconocenes–ethene polymerization catalysts derived from related bridged and open metallocenes

  摘要：

  Condensation of allylcyclopentadiene 1 with acetone in the presence of pyrrolidine gave 2-allyl-6,6-dimethylfulvene (2). Methyllithium addition gave lithium 1-allyl-3-tert-butylcyclopentadienide (3). Transmetallation with 0.5 equiv. of ZrCl4 yielded the respective functionalized zirconocene dichloride complexes meso-4 and rac-4, which were both isolated isomerically pure. With 10 mol% of [Cl2(PCy3)2RuCHPh] the rac-4 diastereoisomer underwent a clean intramolecular ring-closing olefin metathesis reaction to yield the ansa-zirconocene complex rac-6. The complexes meso-4, rac-4 and rac-6 were characterized by X-ray diffraction. Treatment of the open metallocenes meso-4 and rac-4, respectively, with excess methylalumoxane gave rather active ethene polymerization catalysts. The corresponding catalyst derived from the conformationally restricted bulky ansa-metallocene rac-6 is markedly less active.

  DOI：

  10.1039/b911218a
• 作为产物：
  描述：

  sodium cyclopentadienide 、 3-溴丙烯 、 丙酮 在 四氢吡咯 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 4.0h， 生成 2-allyl-6,6-dimethylfulvene
  参考文献：
  名称：

  Ring-closing metathesis of sterically congested functionalized zirconocenes–ethene polymerization catalysts derived from related bridged and open metallocenes

  摘要：

  Condensation of allylcyclopentadiene 1 with acetone in the presence of pyrrolidine gave 2-allyl-6,6-dimethylfulvene (2). Methyllithium addition gave lithium 1-allyl-3-tert-butylcyclopentadienide (3). Transmetallation with 0.5 equiv. of ZrCl4 yielded the respective functionalized zirconocene dichloride complexes meso-4 and rac-4, which were both isolated isomerically pure. With 10 mol% of [Cl2(PCy3)2RuCHPh] the rac-4 diastereoisomer underwent a clean intramolecular ring-closing olefin metathesis reaction to yield the ansa-zirconocene complex rac-6. The complexes meso-4, rac-4 and rac-6 were characterized by X-ray diffraction. Treatment of the open metallocenes meso-4 and rac-4, respectively, with excess methylalumoxane gave rather active ethene polymerization catalysts. The corresponding catalyst derived from the conformationally restricted bulky ansa-metallocene rac-6 is markedly less active.

  DOI：

  10.1039/b911218a

文献信息

• Ring-closing metathesis of sterically congested functionalized zirconocenes–ethene polymerization catalysts derived from related bridged and open metallocenes
  作者：Tülay Aslı Tumay、Gerald Kehr、Roland Fröhlich、Gerhard Erker

  DOI：10.1039/b911218a

  日期：——

  Condensation of allylcyclopentadiene 1 with acetone in the presence of pyrrolidine gave 2-allyl-6,6-dimethylfulvene (2). Methyllithium addition gave lithium 1-allyl-3-tert-butylcyclopentadienide (3). Transmetallation with 0.5 equiv. of ZrCl4 yielded the respective functionalized zirconocene dichloride complexes meso-4 and rac-4, which were both isolated isomerically pure. With 10 mol% of [Cl2(PCy3)2RuCHPh] the rac-4 diastereoisomer underwent a clean intramolecular ring-closing olefin metathesis reaction to yield the ansa-zirconocene complex rac-6. The complexes meso-4, rac-4 and rac-6 were characterized by X-ray diffraction. Treatment of the open metallocenes meso-4 and rac-4, respectively, with excess methylalumoxane gave rather active ethene polymerization catalysts. The corresponding catalyst derived from the conformationally restricted bulky ansa-metallocene rac-6 is markedly less active.