2,12-Dioxabicyclo[11.2.2]heptadeca-1(15),13,16-trien-14-yl(diphenyl)methanol

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,12-Dioxabicyclo[11.2.2]heptadeca-1(15),13,16-trien-14-yl(diphenyl)methanol
• 英文别名: 2,12-dioxabicyclo[11.2.2]heptadeca-1(15),13,16-trien-14-yl(diphenyl)methanol
• 化学式: C₂₈H₃₂O₃
• 分子量: 416.56
• InChiKey: KDQSTXZYFIPZBT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  31
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  1,11-二氧[11]对环芳烷 、 二苯甲酮 在 仲丁基锂 、 鹰爪豆碱 作用下， 以 乙醚 为溶剂， 反应 2.0h， 以84%的产率得到2,12-Dioxabicyclo[11.2.2]heptadeca-1(15),13,16-trien-14-yl(diphenyl)methanol
  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.
• Asymmetric ortho-lithiation of 1,n-dioxa[n]paracyclophane derivatives for the generation of planar chirality
  作者：Kazumasa Kanda、Risa Hamanaka、Kohei Endo、Takanori Shibata

  DOI：10.1016/j.tet.2011.12.031

  日期：2012.2

  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.