(Sp)-13-amino-4-bromo[2.2]paracyclophane

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: (Sp)-13-amino-4-bromo[2.2]paracyclophane
• 英文别名: 4,13-bromo[2.2]paracyclophane amine；4(2)-Bromo-1,4(1,4)-dibenzenacyclohexaphan-1(2)-amine；12-bromotricyclo[8.2.2.24,7]hexadeca-1(12),4,6,10,13,15-hexaen-5-amine
• 化学式: C₁₆H₁₆BrN
• 分子量: 302.214
• InChiKey: GBLHBYBIRQCNHI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  26
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (Sp)-13-amino-4-bromo[2.2]paracyclophane 在 potassium fluoride 、 dihydroxyborane 作用下， 以 1,4-二氧六环 为溶剂， 生成 4-amino[2.2]paracyclophane
  参考文献：
  名称：

  用于铑催化不对称芳基化的平面手性[2.2]对环芳基咪唑并[1,5-a]吡啶盐的合成

  摘要：

  摘要 以(4S p,13R p)-(-)-4-氨基-13-溴[2.2]对环芳烷和吡啶醛为原料合成了几种新型柔性受限的咪唑并[1,5-a]吡啶鎓三氟甲磺酸盐（简称咪唑鎓盐）。 . 这些咪唑鎓盐可用作不对称催化中的含氮杂环卡宾前体，在此它们用于 Rh 催化的芳基硼酸与醛的不对称 1,2-加成反应。在优化催化条件和测试一系列底物后，获得了适中的对映选择性和良好的产率。图形概要

  DOI：

  10.1080/00397911.2011.610548
• 作为产物：
  描述：

  4,15-dibromo[2.2]paracyclophane 在 ammonium hydroxide 、 copper(l) iodide 、 potassium carbonate 、 4-hydroxyproline 作用下， 以 二甲基亚砜 为溶剂， 反应 12.0h， 以56%的产率得到(Sp)-13-amino-4-bromo[2.2]paracyclophane
  参考文献：
  名称：

  Solid-State Emissive Triarylborane-Based [2.2]Paracyclophanes Displaying Circularly Polarized Luminescence and Thermally Activated Delayed Fluorescence

  摘要：

  New types of [2.2]paracyclophane derivatives, g-BNMe2-Cp and mBNMe(2)-Cp, in which electron-donating NMe2 and the electron-accepting BMes(2) are introduced at the pseudo-gem and pseudo-meta positions, were designed and synthesized. The efficient through-space charge transfer enables the intense fluorescence with thermally activated delayed fluorescence characteristics. The quantum yields are up to 0.72 and 0.39 in cyclohexane. In addition, no significant fluorescence quenching was observed in the solid state with fluorescence quantum yields of powder up to 0.53 and 0.33. Moreover, the enantiomerically pure forms of g-BNMe2-Cp exhibit strong CPL signals with g(lum) up to 4.24 X 10(-3).

  DOI：

  10.1021/acs.orglett.8b02995

文献信息

• The synthesis of planar chiral pseudo-gem aminophosphine pre-ligands based on [2.2]paracyclophane
  作者：Krishanthi P. Jayasundera、Tim G. W. Engels、David J. Lun、Maulik N. Mungalpara、Paul G. Plieger、Gareth J. Rowlands

  DOI：10.1039/c7ob02393f

  日期：——

  The synthesis of three planar chiral pseudo-gem disubstituted [2.2]paracyclophane-derived P,N-pre-ligands is reported along with preliminary results of their activity in the amination of aryl bromides and chlorides. The pseudo-gem aminophosphines were capable of mediating the coupling reaction at a loading of 1 mol%.

  报道了三种平面手性假宝石双取代的[2.2]对环环烷衍生的P，N-预配体的合成以及它们在芳基溴化物和氯化物的胺化中的活性的初步结果。所述伪宝石氨基膦为能够介导在1摩尔％的负载的偶联反应的。
• Synthesis of Enantiopure Planar-Chiral Thiourea Derivatives
  作者：Jan Paradies、Jakob Schneider、Roland Fröhlich

  DOI：10.1055/s-0030-1258205

  日期：2010.10

  employed in cross-coupling reactions to yield arylated 4-amino[2.2]paracyclophanes. The amines were converted into enantiopure planar-chiral thioureas, which are potential hydrogen-bond donors for enantioselective organocatalysis. thiourea - hydrogen-bond donor - planar-chiral - cross-coupling

  描述了有效获取对映体纯的伪双取代的4-氨基-13-溴[2.2]对环环烷的方法。氨基溴化物用于交叉偶联反应中，生成芳基化的4-氨基[2.2]对环环烷。胺被转化为对映纯的平面手性硫脲，它们是对映选择性有机催化的潜在氢键供体。 硫脲-氢键供体-平面手性-交叉偶联
• Synthesis of planar chiral [2.2]paracyclophane Schiff bases for the enantioselective Henry reaction
  作者：Fuyan He、Yudao Ma、Lei Zhao、Wenzeng Duan、Jianqiang Chen、Zhongxi Zhao

  DOI：10.1016/j.tetasy.2012.06.005

  日期：2012.6

  A series of diastereomerically pure Schiff base ligands based on [2.2]paracyclophane backbones were synthesized and separated. The new planar chiral [2.2]paracyclophane Schiff bases were used as ligands in Cu-catalyzed asymmetric Henry reactions with high yields and enantioselectivities.

  合成并分离了基于[2.2]对环环烷骨架的一系列非对映体纯的席夫碱配体。新的平面手性[2.2]对环环烷席夫碱被用作铜催化的不对称亨利反应中的配体，具有高收率和对映选择性。
• The synthesis of substituted amino[2.2]paracyclophanes
  作者：Krishanthi P. Jayasundera、Disraëli N. M. Kusmus、Lise Deuilhé、Leonie Etheridge、Zane Farrow、David J. Lun、Gurpreet Kaur、Gareth J. Rowlands

  DOI：10.1039/c6ob02150f

  日期：——

  Two methodologies for the formation of substituted amino[2.2]paracyclophane derivatives were developed. The first involves the direct amination of bromo[2.2]paracyclophanes with sodium azide. This permits the synthesis of simple mono- and disubstituted derivatives but fails to give sterically congested pseudo-gem derivatives. A ‘one-pot’ oxidation-Lossen rearrangement of [2.2]paracyclophane oximes

  开发了两种形成取代的氨基[2.2]对环环烷衍生物的方法。第一种方法涉及用叠氮化钠直接胺化溴化[2.2]对环环烷。这允许合成简单的单取代和二取代的衍生物，但不能产生在空间上拥挤的伪宝石衍生物。[2.2]对环环肟肟的“一锅法”氧化-洛森重排提供了对氨基[2.2]对环环糊精的访问，包括迄今为止报道的最有效的伪宝石平面手性氨基酸的合成。
• Planar Chirality Change in Dediazoniation Reactions of Paracyclophanes and Mechanistic Implication
  作者：Fuyan He、Yudao Ma、Lei Zhao、Wenzeng Duan、Jianqiang Chen、Chun Song

  DOI：10.1021/ol302510t

  日期：2012.11.2

  Dediazoniation reactions of (Sp)-4-bromo-13-[2.2]paracyclophanyldiazonium fluoborate 2a through a heterolytic cleavage process gave products with partial racemization. In contrast, dediazoniation reactions of (Sp)-2a undergoing a nonheterolytic cleavage process afforded products with retention of configuration. A key intermediate, the bromonium cation B, caused the racemization. The unexpected racemization

  （S p）-4-溴-13- [2.2]对环吡啶基重氮氟硼酸酯2a通过杂解裂解反应进行脱氮反应，得到部分消旋的产物。与此相反，（的dediazoniation反应小号p） - 2a中经历nonheterolytic裂解方法得到的产品具有配置的保持。关键中间体溴阳离子B引起了外消旋作用。出乎意料的消旋作用允许探究脱氮反应的机理。