4-N-(phenyl)amino-[2.2]paracyclophane | 1370794-74-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-N-(phenyl)amino-[2.2]paracyclophane
• 英文别名: N-phenyltricyclo[8.2.2.24,7]hexadeca-1(13),4,6,10(14),11,15-hexaen-5-amine
• CAS: 1370794-74-3
• 化学式: C₂₂H₂₁N
• 分子量: 299.415
• InChiKey: RWIQYXQGBDEXDU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.31
• 重原子数：
  23.0
• 可旋转键数：
  2.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  12.03
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  4-N-(phenyl)amino-[2.2]paracyclophane 在 palladium diacetate 、 三甲基乙酸 作用下， 以 溶剂黄146 为溶剂， 反应 8.0h， 以62%的产率得到[2]paracyclo[2](1,4)carbazolophane
  参考文献：
  名称：

  合成具有[2.2]环芳烷骨架的平面手性咔唑衍生物

  摘要：

  描述了带有[2.2]对环环烷骨架的平面手性咔唑的合成。由Pd催化的C2.2N交叉偶联和随后的氧化环化反应通过两步合成，从容易获得的4-溴[2.2]对环环烷平面手性咔唑开始。

  DOI：

  10.1002/ijch.201100070
• 作为产物：
  描述：

  4-溴[2.2]对环芳烷 、 苯胺 在 tris-(dibenzylideneacetone)dipalladium(0) 、 sodium t-butanolate 、 2-二环己基磷-2,4,6-三异丙基联苯 作用下， 以 甲苯 为溶剂， 反应 4.5h， 以81%的产率得到4-N-(phenyl)amino-[2.2]paracyclophane
  参考文献：
  名称：

  合成具有[2.2]环芳烷骨架的平面手性咔唑衍生物

  摘要：

  描述了带有[2.2]对环环烷骨架的平面手性咔唑的合成。由Pd催化的C2.2N交叉偶联和随后的氧化环化反应通过两步合成，从容易获得的4-溴[2.2]对环环烷平面手性咔唑开始。

  DOI：

  10.1002/ijch.201100070

文献信息

• Phenyliodine Diacetate-Mediated<i>para</i>-Functionalizations of Amido- and Amino-Substituted [2.2]Paracyclophanes
  作者：Petra Schaal née Lennartz、Hannah Baars、Gerhard Raabe、Iuliana Atodiresei、Carsten Bolm

  DOI：10.1002/adsc.201300547

  日期：2013.9.16

  The reaction of N‐[2.2]paracyclophanyl‐substituted amides or amines with phenyliodine diacetate (PIDA) and protic nucleophiles affords mixed para‐substituted [2.2]paracyclophane derivatives in moderate to good yields. As protic nucleophiles carboxylic acids and alcohols as well as pyridine hydrobromide can be used. 4‐Hydroxy[2.2]paracyclophane reacts in an analogous manner.

  的反应ñ - [2.2] paracyclophanyl取代酰胺或胺与phenyliodine二乙酸酯（PIDA）和质子亲核试剂混合，得到对位-取代的[2.2]对环芳烷衍生物在中度至良好的产率。作为质子亲核试剂，可以使用羧酸和醇以及吡啶氢溴酸盐。4-羟基[2.2]对环环烷类以相似的方式反应。
• Combined Theoretical and Experimental Study on High Diastereoselective Chirality Transfer Based on [2.2]Paracyclophane Derivative Chiral Reagent
  作者：Biao Jiang、Lei Han、Yong-Le Li、Xiao-Long Zhao、Yang Lei、Dai-Qian Xie、John Z. H. Zhang

  DOI：10.1021/jo202186e

  日期：2012.2.17

  We report a paracyclophane N-Me thioamide chiral reagent for the asymmetric thio-Claisen rearrangement with high diasteroselectivity. Comparisons between candidate chiral reagent N-phenyl-N-([2.2]paracyclophan-4-yl)amide, N-methyl amide, N-phenyl thioamide, and N-methyl thioamide are made both by experiment and theoretical calculations to clarify the principle behind the high diasteroselectivity. Dynamic H-1 NMR phenomenon tested by varying temperature (VT) experiments has proved that N-Ph amides have triple splitting peaks, while N-Ph thioamide would reduce the number to two, further substituting the Ph to Me made dynamic phenomenon disappear. So the side chain is thought to be the most rigid in N-Me thioamide, which accounts for a structure prerequisite favoring high efficient chirality transfer. This is confirmed by theoretical calculation: remarkable energy difference exists between the Re and Si faces of the chiral molecule. To further clarify the possible pathways for thio-Claisen rearrangement, theoretical prediction is adopted. The result implies that the cisoid pathways will dominate the process. Further experiment confirmed this: with N-Me thioamide, the asymmetrical reaction affords gamma-unsaturated thioamides in good yields and high diastereoselectivities up to 98%. After removing the thioamide auxiliaries under hydrolysis conditions, product beta,gamma-substituted chiral alcohols reached high enantiopurity of 98% ee.