cis-8-bis(cyclopentadienyl)zirconabicyclo[4.3.0]nonane

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: cis-8-bis(cyclopentadienyl)zirconabicyclo[4.3.0]nonane
• 英文别名: cis-Cp2(zirconahydrindane)
• 化学式: C₁₈H₂₄Zr
• 分子量: 331.613
• InChiKey: RUNKQYSHMDRTTQ-UZCMYEMWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.09
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  cis-8-bis(cyclopentadienyl)zirconabicyclo[4.3.0]nonane 以 not given 为溶剂， 以>99的产率得到trans-8-bis(cyclopentadienyl)zirconabicyclo[4.3.0]nonane
  参考文献：
  名称：

  Template synthesis of substituted cyclopentanones by zirconocene/olefin/CO systems

  摘要：

  A series of 3,4-dialkylcyclopentanones was synthesized by template reactions on the "Cp2Zr" moiety generated from Cp2Zr(2,4-hexadiene) or Cp2Zr(olefin) complexes by ligand exchange reactions. The addition of a 1-olefin or 1,7-octadiene to the Cp2Zr species followed by CO insertion and acid hydrolysis gave a cis- or trans-disubstituted cyclopentanone in high yield.

  DOI：

  10.1016/s0277-5387(00)83539-1
• 作为产物：
  描述：

  Cp2Zr((E,E)-2,4-hexadiene) 、 1,7-辛二烯 以 苯 为溶剂， 生成 cis-8-bis(cyclopentadienyl)zirconabicyclo[4.3.0]nonane
  参考文献：
  名称：

  Template synthesis of substituted cyclopentanones by zirconocene/olefin/CO systems

  摘要：

  A series of 3,4-dialkylcyclopentanones was synthesized by template reactions on the "Cp2Zr" moiety generated from Cp2Zr(2,4-hexadiene) or Cp2Zr(olefin) complexes by ligand exchange reactions. The addition of a 1-olefin or 1,7-octadiene to the Cp2Zr species followed by CO insertion and acid hydrolysis gave a cis- or trans-disubstituted cyclopentanone in high yield.

  DOI：

  10.1016/s0277-5387(00)83539-1

文献信息

• Monohalogenation of Zirconacyclopentane Complexes via Alkylalkoxyzirconocene
  作者：Tamotsu Takahashi、Koichiro Aoyagi、Ryuichiro Hara、Noriyuki Suzuki

  DOI：10.1246/cl.1992.1693

  日期：1992.9

  butene-butene coupling product on zirconium, with methanol followed by bromine gave selectively monobromination product, 2-ethyl-3-methyl-1-bromopentane, in 89% yield with high stereoselectivity. Similarly, non-conjugated diene cyclization products on zirconium were also selectively converted into monohalogenated compounds. These selective monohalogenations proceeded via alkylalkoxyzirconocene complexes

  用甲醇和溴处理反式-3,4-二乙基锆并环戊烷络合物（锆上的选择性丁烯-丁烯偶联产物）得到选择性单溴化产物 2-乙基-3-甲基-1-溴戊烷，产率为 89%高立体选择性。同样，锆上的非共轭二烯环化产物也被选择性地转化为单卤代化合物。这些选择性单卤化反应是通过烷基烷氧基锆茂配合物进行的。
• Preparation of zirconium(II) complexes by ligand-induced reductive elimination. Bis(.eta.5-cyclopentadienyl)bis(phosphine)zirconium(II) complexes and their reactions
  作者：Kerrie I. Gell、Jeffrey Schwartz

  DOI：10.1021/ja00400a033

  日期：1981.5
• Zirconium-catalyzed and zirconium-promoted cyclization reactions of non-conjugated dienes with alkylmagnesium halides to give cycloalkylmethylmagnesium derivatives
  作者：Ei-ichi Negishi、Christophe J. Rousset、Danièle Choueiry、John P. Maye、Noriyuki Suzuki、Tamotsu Takahashi

  DOI：10.1016/s0020-1693(98)00064-4

  日期：1998.10

  The stoichiometric reaction of certain non-conjugated dienes with n-Bu2ZrCp3 provides the corresponding zirconabicycles, such as trans-3-bis( cyclopentadienyl) zirconabicyclo [3.3.0] octane, that can be fully characterized by spectroscopic means. Their treatment with EtMgBr or n-BuMgCl in THF gives The corresponding monocyclic monomagnesium derivatives along with the corresponding alkene-ZrCp2 derivatives in high yields. In cases where the Grignard reagent is either sterically hindered or lacking P-HI little or no reaction may occur, although some, e.g., s-BuMgCl, react, albeit slowly, to give the expected products in high yields. In cases where either a Grignard reagent in diethyl ether or a dialkylmagnesium (irrespective of solvent) is used, the major product is the corresponding dimagnesio derivative. A couple of intramolecular transmetallation paths are proposed for these cases. The Cp2ZrCl2-catalyzed reaction of 1,6-heptadiene with EtMgBr fails to induce the desired bicyclization-ring opening sequence to give the corresponding monocyclic monomagnesium derivatives. On the other hand, the corresponding reaction with n-BuMgBr does proceed as desired to give the monocyclic monomagnesium product which contains a minor amount of the corresponding exo-methylene derivative. Only traces, if any, of the corresponding dimagnesium derivatives reported to be the major products in Et2O are formed. This procedure has been applied to catalytically convert several other dienes, i.e., (E)-1-phenyl-1,6-heptadiene, 2,4,4-trimethyl-1,6-heptadiene, diallyl (benzyl) amine, 1,7-octadiene and 1,2-diallylbenzene, into the corresponding monocyclized compounds in moderate to excellent combined yields. (C) 1998 Elsevier Science S.A. All rights reserved.
• Template synthesis of substituted cyclopentanones by zirconocene/olefin/CO systems
  作者：Munetaka Akita、Hajime Yasuda、Hitoshi Yamamoto、Akira Nakamura

  DOI：10.1016/s0277-5387(00)83539-1

  日期：1991.1

  A series of 3,4-dialkylcyclopentanones was synthesized by template reactions on the "Cp2Zr" moiety generated from Cp2Zr(2,4-hexadiene) or Cp2Zr(olefin) complexes by ligand exchange reactions. The addition of a 1-olefin or 1,7-octadiene to the Cp2Zr species followed by CO insertion and acid hydrolysis gave a cis- or trans-disubstituted cyclopentanone in high yield.