(1R,5R,8R,9S,11S)-1,5,14,14,15,15-hexamethylpentacyclo<9.2.1.15,8.02,10.04,9>pentadeca-3,Δ2,10-diene | 126035-88-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1R,5R,8R,9S,11S)-1,5,14,14,15,15-hexamethylpentacyclo<9.2.1.15,8.02,10.04,9>pentadeca-3,Δ2,10-diene
• 英文别名: (1R,5R,8R,9S,11S)-1,5,14,14,15,15-hexamethylpentacyclo<9.2.1.1^5,8.0^2,10.0^4,9>pentadeca-3,Δ^2,10-diene；(1R,5R,8R,9S,11S)-1,5,14,14,15,15-hexamethylpentacyclo[9.2.1.1^5,8.0^2,10.0^4,9]pentadeca-3,Δ^2,10-diene
• CAS: 126035-88-9
• 化学式: C₂₁H₃₀
• 分子量: 282.469
• InChiKey: JSCXNLGZCCCCCQ-IXAODXNMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.75
• 重原子数：
  21.0
• 可旋转键数：
  0.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  (1R,5R,8R,9S,11S)-1,5,14,14,15,15-hexamethylpentacyclo<9.2.1.15,8.02,10.04,9>pentadeca-3,Δ2,10-diene 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 48.0h， 生成 (1R,5R,8S,11S)-1,5,14,14,15,15-hexamethylpentacyclo<9.2.1.1^5,8.0^2,10.0^4,9>pentadeca-3,Δ^2,10-dienyllithium
  参考文献：
  名称：

  On the structural features of the chiral organometallic Lewis-acid catalyst “(dibornacyclopentadienyl)zirconiumtrichloride”

  摘要：

  2-Bornenyllithium (3) was prepared from camphor by a variant of the Shapiro reaction and then reacted with 0.5 molar equivalents of ethylformate to give the dibornenylcarbinol 4. Subsequent acid-catalyzed cyclization of 4 yielded ''dibornacyclopentadiene'' as a mixture of two diastereoisomers; their deprotonation with n-butyllithium produced a single ''dibornacyclopentadienyllithium'' reagent (6). Reaction of 6 with MCl4 (M = Zr, Hf, Ti) gave the chiral organometallic Lewis-acids ''(diborna-CP)MCl3''. ''(+)-(Dibornacyclopentadienyl)zirconiumtrichloride'' (7a) was characterized by X-ray diffraction. The molecular structure of 7a provides a basis for discussing the stereochemical characteristics of the enantioselective arene hydroxyalkylation process catalyzed by the optically active organometallic Lewis-acid ''(dibornacyclopentadienyl)zirconiumtrichloride''.

  DOI：

  10.1016/0022-328x(93)86061-l
• 作为产物：
  描述：

  (+)-(1R,4R)-1,7,7-trimethylbicyclo<2.2.1>heptan-2-one-(2,4,6-triisopropylbenzene-sulfonylhydrazone) 在 potassium hydrogensulfate 、 仲丁基锂 作用下， 反应 5.33h， 生成 (1R,5R,8R,9S,11S)-1,5,14,14,15,15-hexamethylpentacyclo<9.2.1.15,8.02,10.04,9>pentadeca-3,Δ2,10-diene
  参考文献：
  名称：

  On the structural features of the chiral organometallic Lewis-acid catalyst “(dibornacyclopentadienyl)zirconiumtrichloride”

  摘要：

  2-Bornenyllithium (3) was prepared from camphor by a variant of the Shapiro reaction and then reacted with 0.5 molar equivalents of ethylformate to give the dibornenylcarbinol 4. Subsequent acid-catalyzed cyclization of 4 yielded ''dibornacyclopentadiene'' as a mixture of two diastereoisomers; their deprotonation with n-butyllithium produced a single ''dibornacyclopentadienyllithium'' reagent (6). Reaction of 6 with MCl4 (M = Zr, Hf, Ti) gave the chiral organometallic Lewis-acids ''(diborna-CP)MCl3''. ''(+)-(Dibornacyclopentadienyl)zirconiumtrichloride'' (7a) was characterized by X-ray diffraction. The molecular structure of 7a provides a basis for discussing the stereochemical characteristics of the enantioselective arene hydroxyalkylation process catalyzed by the optically active organometallic Lewis-acid ''(dibornacyclopentadienyl)zirconiumtrichloride''.

  DOI：

  10.1016/0022-328x(93)86061-l

文献信息

• Optically Pure <i>C</i>₂-Symmetric Transition Metal Complexes. Steric Consequences of Flanking the Cyclopentadienyl Anion with a Pair of Bridged Bicyclic Terpene-Derived Hydrocarbon Subunits
  作者：Leo A. Paquette、Eugene I. Bzowej、Rüdiger Kreuzholz

  DOI：10.1021/om960391j

  日期：1996.10.29

  generalized to encompass two related cyclopentadienes flanked by bridged bicyclic subunits derived from (1R)-(+)-verbenone (4). Whereas lithium dimethylcuprate addition to 4 leads to 5a, reaction with diisobutylaluminum hydride and methylcopper affords the less substituted analog 5b. Both saturated ketones undergo the Shapiro reaction and subsequent in situ condensation with ethyl formate to deliver the

  Erker开发的用于制备“二烯丙基环戊二烯” 1的方​​法已被概括为涵盖两个相关的环戊二烯，其侧翼是衍生自（1 R）-（+）-马来酮（4）的桥连双环亚基。将二甲基铜碳酸锂加到4中则生成5a，与二异丁基氢化铝和甲基铜反应得到较少取代的类似物5b。两种饱和酮均发生Shapiro反应，随后与甲酸乙酯原位缩合以生成二烯醇7a，b， 分别。这些中间体的脱水环化比以前涉及1的工作更难完成。在25°C下将7a暴露于苯中的樟脑磺酸中，产率为82％，得到8。这些条件证明对于7b来说太苛刻了，然而7b却进行了闭环反应，在乙醚中生成9（68％）的碘。在去质子化之后，可以将8甲硅烷基化得到11，但是环戊二烯酸锂和硅烷都不能被诱使形成各种钛茂或锆茂复合物。因此，这些反应物在空间上必须比1更拥挤。，它的确与MCl 4（Erker）和CpTiCl 3 3反应（这项工作）。显着地，烃9完全抵抗去质子化，这直接反映了在其sp
• Erker, Gerhard; Zeijden, Adolphus A. H. van der, Angewandte Chemie, 1990, vol. 102, # 5, p. 543 - 545
  作者：Erker, Gerhard、Zeijden, Adolphus A. H. van der

  DOI：——

  日期：——