6-{2-[bis(but-2-ynyl)amino]phenoxy}hexanenitrile | 1186029-72-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 6-{2-[bis(but-2-ynyl)amino]phenoxy}hexanenitrile
• 英文别名: 6-[2-[Bis(but-2-ynyl)amino]phenoxy]hexanenitrile；6-[2-[bis(but-2-ynyl)amino]phenoxy]hexanenitrile
• CAS: 1186029-72-0
• 化学式: C₂₀H₂₄N₂O
• 分子量: 308.423
• InChiKey: JVQLERGRDCUATF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  36.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  6-{2-[bis(but-2-ynyl)amino]phenoxy}hexanenitrile 在 bis(1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 2.0h， 以52%的产率得到(R)-2,6-(1,2-o-benzo-3-oxaoctano)-2,3-dihydro-4,7-dimethyl-1H-pyrrolo[3,4-c]pyridine
  参考文献：
  名称：

  通过[2 + 2 + 2]支链Triynes的环加成反应，手性三脚架笼化合物的对映选择性合成

  摘要：

  由2-氨基苯酚的氮原子分支的三炔的三环环化反应产生平面手性三脚架笼状化合物。当使用阳离子Rh-Me-DUPHOS催化剂时，可以高收率和优异的ee获得环加合物，还可以获得具有[15]环烷体系的大环化合物。通过二炔-腈的分子内反应，该方法可以进一步应用于三臂吡啶的合成。

  DOI：

  10.1021/ol9014893
• 作为产物：
  描述：

  6-溴己腈 在 sodium hydride 、 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 生成 6-{2-[bis(but-2-ynyl)amino]phenoxy}hexanenitrile
  参考文献：
  名称：

  Enantioselective synthesis of tripodal cyclophanes and pyridinophanes by intramolecular [2+2+2] cycloaddition

  摘要：

  An enantioselective intramolecular [2+2+2] cycloaddition of 2-aminophenol-tethered triynes and diyne-nitriles proceeded using the chiral Rh catalysts, and tripodal cyclophanes and pyridinophanes with a long ansa chain (up to [16]pyridinophane) were obtained in acceptable yield with high to almost perfect ee. In the reaction of triynes, we elucidated that the oxygen atom at the alkyne terminus is essential for the excellent enantioselectivity. For the construction of cage-type molecule, the choice of rigid tether, which connects 1,6-diyne moiety with a side carbon chain having alkyne or cyano group on its terminus, was important, and 8-amino-2-naphthol moiety was also a preferable tether. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.01.046

文献信息

• Enantioselective Synthesis of Chiral Tripodal Cage Compounds by [2 + 2 + 2] Cycloaddition of Branched Triynes
  作者：Takanori Shibata、Toshifumi Uchiyama、Kohei Endo

  DOI：10.1021/ol9014893

  日期：2009.9.3

  Cyclotrimerization of triynes branched by a nitrogen atom of 2-aminophenol yielded planar-chiral tripodal cage compounds. When a cationic Rh−Me-DUPHOS catalyst was used, the cycloadducts were obtained in high yield and excellent ee, and a macrocyclic compound with a [15]cyclophane system was also obtained. This method can be further applied to the synthesis of a triarmed pyridinophane by the intramolecular

  由2-氨基苯酚的氮原子分支的三炔的三环环化反应产生平面手性三脚架笼状化合物。当使用阳离子Rh-Me-DUPHOS催化剂时，可以高收率和优异的ee获得环加合物，还可以获得具有[15]环烷体系的大环化合物。通过二炔-腈的分子内反应，该方法可以进一步应用于三臂吡啶的合成。
• Enantioselective synthesis of tripodal cyclophanes and pyridinophanes by intramolecular [2+2+2] cycloaddition
  作者：Takanori Shibata、Mayu Miyoshi、Toshifumi Uchiyama、Kohei Endo、Nobuaki Miura、Kenji Monde

  DOI：10.1016/j.tet.2012.01.046

  日期：2012.3

  An enantioselective intramolecular [2+2+2] cycloaddition of 2-aminophenol-tethered triynes and diyne-nitriles proceeded using the chiral Rh catalysts, and tripodal cyclophanes and pyridinophanes with a long ansa chain (up to [16]pyridinophane) were obtained in acceptable yield with high to almost perfect ee. In the reaction of triynes, we elucidated that the oxygen atom at the alkyne terminus is essential for the excellent enantioselectivity. For the construction of cage-type molecule, the choice of rigid tether, which connects 1,6-diyne moiety with a side carbon chain having alkyne or cyano group on its terminus, was important, and 8-amino-2-naphthol moiety was also a preferable tether. (C) 2012 Elsevier Ltd. All rights reserved.