2-[5-(6,6-Dimethyl-4,8-dioxaspiro[2.5]oct-1-en-2-yl)pentyl]-6,6-dimethyl-4,8-dioxaspiro[2.5]oct-1-ene | 181883-63-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-[5-(6,6-Dimethyl-4,8-dioxaspiro[2.5]oct-1-en-2-yl)pentyl]-6,6-dimethyl-4,8-dioxaspiro[2.5]oct-1-ene
• CAS: 181883-63-6
• 化学式: C₂₁H₃₂O₄
• 分子量: 348.483
• InChiKey: DXVQKWQRKWGTJU-UHFFFAOYSA-N

物化性质

• 沸点：
  443.7±45.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-[5-(6,6-Dimethyl-4,8-dioxaspiro[2.5]oct-1-en-2-yl)pentyl]-6,6-dimethyl-4,8-dioxaspiro[2.5]oct-1-ene 在 palladium dichloride copper(I) trifluoromethanesulfonate benzene 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以20%的产率得到1,4-bis(2,2-dimethyl-3-hydroxypropoxycarbonyl)-(E)-1,(E)-3-cyclononadiene
  参考文献：
  名称：

  Macrocarbocycle Synthesis by Copper- and Silver-Mediated Cyclization of Tethered Cyclopropenone Acetals. Electronic Tuning of Metal Vinylcarbene Complex into Vinylmetallic Species

  摘要：

  [GRAPHICS]Synthesis of n-membered medium and macrocarbocycles through intramolecular sp(2)-sp(2) C-C bond formation was achieved with the aid of CuOTf or AgOTf by intramolecular coupling reaction of cyclopropenone acetals tethered by a methylene chain of (n - 4) carbon atoms, The reaction has proved to be useful for the synthesis of large carbocycles (n > 13) in yields as high as 78%, and most notably also for an eight-membered carbocycle in 88% yield.

  DOI：

  10.1021/ol990053p
• 作为产物：
  描述：

  6,6-二甲基-4,8-二氧杂螺[2.5]辛-1-烯 、 1,5-二碘戊烷 在 六甲基磷酰三胺 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 11.0h， 以76%的产率得到2-[5-(6,6-Dimethyl-4,8-dioxaspiro[2.5]oct-1-en-2-yl)pentyl]-6,6-dimethyl-4,8-dioxaspiro[2.5]oct-1-ene
  参考文献：
  名称：

  Macrocarbocycle Synthesis by Copper- and Silver-Mediated Cyclization of Tethered Cyclopropenone Acetals. Electronic Tuning of Metal Vinylcarbene Complex into Vinylmetallic Species

  摘要：

  [GRAPHICS]Synthesis of n-membered medium and macrocarbocycles through intramolecular sp(2)-sp(2) C-C bond formation was achieved with the aid of CuOTf or AgOTf by intramolecular coupling reaction of cyclopropenone acetals tethered by a methylene chain of (n - 4) carbon atoms, The reaction has proved to be useful for the synthesis of large carbocycles (n > 13) in yields as high as 78%, and most notably also for an eight-membered carbocycle in 88% yield.

  DOI：

  10.1021/ol990053p

文献信息

• Synthetic and Computational Studies on Symmetry-Defined Double Cycloaddition of a New Tris-Annulating Reagent to C₆₀
  作者：Hiroyuki Isobe、Hidetoshi Tokuyama、Masaya Sawamura、Eiichi Nakamura

  DOI：10.1021/jo970685u

  日期：1997.7.1

  For the purpose of doubly functionalizing fullerenes, new tris-annulating reagents 2(n) have been developed. The reagents carry, in one molecule, two cyclopropenone acetals which are connected with an n-carbon methylene tether. Upon thermolysis of 2(n) in the presence of C-60, the reagent undergoes [3 + 2] cycloaddition reaction twice in a regio- and stereoselective manner to give C-s and C-2 organofullerenes bearing two cyclopentenone acetals. The selectivity varies as the function of the tether structure. The experiments have shown that, in each series of different tether lengths, one can obtain one or two diastereomeric double adducts out of several structural possibilities. The selectivity of the reaction did not conform to the prediction made on the basis of previous knowledge on intermolecular double additions but was found to be correlated to the conformational strain of the tether moiety, which can be estimated by a newly developed ''double differential protocol''. Systematic studies on the reliability of various computational methods for organofullerenes indicated that certain molecular orbital and molecular mechanics calculations give very reliable structural data while certain others do not.