14,17-bis(trimethylsilyl)-1,12-dioxa[12]paracyclophane | 1229009-91-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 14,17-bis(trimethylsilyl)-1,12-dioxa[12]paracyclophane
• 英文别名: 12,15-bis(trimethylsilyl)-2,13-dioxa-1(1,4)-benzenacyclotridecaphane
• CAS: 1229009-91-9
• 化学式: C₂₂H₄₀O₂Si₂
• 分子量: 392.729
• InChiKey: PNVIQDXPNRQBAA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.67
• 重原子数：
  26.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  Dioxa<12>paracyclophane 在 四甲基乙二胺 、 仲丁基锂 、 鹰爪豆碱 作用下， 以 乙醚 为溶剂， 反应 76.0h， 生成 14,17-bis(trimethylsilyl)-1,12-dioxa[12]paracyclophane 、 14,17-bis(trimethylsilyl)-1,12-dioxa[12]paracyclophane
  参考文献：
  名称：

  Asymmetric ortho-lithiation of 1,n-dioxa[n]paracyclophane derivatives for the generation of planar chirality

  摘要：

  The asymmetric induction of planar chirality in 1,n-dioxa[n]paracyclophane derivatives via asymmetric ortho-lithiation is described. Enantioselective ortho-lithiation of unflippable 1,n-dioxa[n]paracyclophanes (n <= 11) using sec-BuLi-(-)-sparteine at -78 degrees C and subsequent treatment with electrophiles gave the corresponding planar-chiral monosubstituted paracyclophanes with excellent ee. Further lithiation of these compounds and treatment with electrophiles gave planar-chiral paracyclophanes with two different substituents. Dilithiation of unflippable 1,n-dioxa[n]paracyclophanes gave the corresponding C(2)symmetrical disubstituted products with almost perfect ee. In the case of flippable 1,n-dioxa[n]paracyclophanes (n >= 12), a stepwise reaction was required for the highly enantioselective formation of disubstituted products. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.12.031

文献信息

• Enantioselective Synthesis of Planar-Chiral 1,<i>n</i>-Dioxa[<i>n</i>]paracyclophanes via Catalytic Asymmetric <i>ortho</i>-Lithiation
  作者：Kazumasa Kanda、Kohei Endo、Takanori Shibata

  DOI：10.1021/ol100444u

  日期：2010.5.7

  Highly enantioselective ortho-lithiation and dilithiation of 1,n-dioxa[n]paracyclophanes were realized with the use of see-butyllithium and a catalytic or stoichiometric amount of sparteine. Quenching with various electrophiles, such as iodine, iodomethane, and chlorodiphenylphosphine, afforded chiral mono- and disubstituted paracyclophanes with good to excellent ee.