1,1-bis(η(5)-pentamethylcyclopentadienyl)-2-methylene-3-tert-butyl-4-(2-tert-butyl-1-ethynyl)titanacyclobutene | 182417-25-0

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 1,1-bis(η(5)-pentamethylcyclopentadienyl)-2-methylene-3-tert-butyl-4-(2-tert-butyl-1-ethynyl)titanacyclobutene
• 英文别名: 3-tert-butyl-7,7-dimethylocta-1,3-dien-5-yne;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;titanium(4+)
• CAS: 182417-25-0
• 化学式: C₃₄H₅₀Ti
• 分子量: 506.651
• InChiKey: DOSNKOBNMDPJIT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  2,2,7,7-四甲基-3,5-辛二炔 、 decamethyltitanocenemethylvinyl 以 正己烷 为溶剂， 以83.1%的产率得到1,1-bis(η(5)-pentamethylcyclopentadienyl)-2-methylene-3-tert-butyl-4-(2-tert-butyl-1-ethynyl)titanacyclobutene
  参考文献：
  名称：

  Regioselective Reactions of 1,3-Diynes with the Titanocene Vinylidene Fragment [Cp*₂TiCCH₂]. Crystal and Molecular Structure of Cp*₂TiC(C⋮CSiMe₃)C(SiMe₃)CCH₂

  摘要：

  The titanocene vinylidene intermediate [Cp*Ti-2=C=CH2] (6)(Cp*: C-5(CH3)5), formed by ethene or methane elimination from Cp*2TiCH2CH2C=CH2 (5) and Cp*Ti-2(CH=CH2)(CH3) (7), respectively, reacts with 1,3-diynes RC=C-C=CR (R = Me (13a), Ph(13b), SiMe(3) (13c), CMe(3) (13d)) by a [2 + 2]-cycloaddition, giving metallacyclobutenes Cp*2TiC(C=CR)=CRC=CH2 (9a-d). Using the unsymmetrical 1,3-diyne RC=CC=CR(1) (R = CMe(3), R(1) = SiMe(3) (13e)), a 9:1 mixture of the metallacyclobutenes Cp*2TiC(C=CR)=CR(1)C=CH2 (9e) and Cp*2TiC-(C=CR(1))=CRC =CH2 (9e') is formed. In all cases, exclusive formation of one regioisomer exhibiting the C=CR substituent in the alpha-position of the metallacycle is observed. The regioselectivity of the formation of 9 is attributed to the polarity of the C=C bond as well as the stereochemical conditions, proven by ab initio calculations at the Hartree-Fock (HF) level of theory with the 3-21G(*) standard basis set and molecular modeling. The X-ray structure of 9c is presented. Subsequent reactions of 9 with an excess of the titanocene intermediate 6, to form binuclear metallacycles, are not observed.

  DOI：

  10.1021/om960591v