14-(trimethylsilyl)-1,12-dioxa[12]paracyclophane | 1356382-75-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 14-(trimethylsilyl)-1,12-dioxa[12]paracyclophane
• 英文别名: 2,13-Dioxabicyclo[12.2.2]octadeca-1(16),14,17-trien-15-yl(trimethyl)silane；2,13-dioxabicyclo[12.2.2]octadeca-1(16),14,17-trien-15-yl(trimethyl)silane
• CAS: 1356382-75-6
• 化学式: C₁₉H₃₂O₂Si
• 分子量: 320.547
• InChiKey: KNNFNHVBABBNAQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.12
• 重原子数：
  22
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  14-(trimethylsilyl)-1,12-dioxa[12]paracyclophane 在 N-溴代丁二酰亚胺(NBS) 、 仲丁基锂 、 鹰爪豆碱 作用下， 以 乙醚 为溶剂， 反应 73.0h， 生成 2,5-dibromo-1,4-(decamethylen-1,10-dioxy)benzene
  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
• 作为产物：
  描述：

  对苯二酚 在 四甲基乙二胺 、 仲丁基锂 、 potassium carbonate 作用下， 以 乙醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 15.0h， 生成 14-(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

• 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.