11,14-Dibromo-phenanthro[3,4-c]phenanthrene

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 11,14-Dibromo-phenanthro[3,4-c]phenanthrene
• 英文别名: 11,14-Dibromophenanthro[3,4-c]phenanthrene；2,15-dibromohexahelicene
• 化学式: C₂₆H₁₄Br₂
• 分子量: 486.205
• InChiKey: MHDVCMHCPVEHDG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.6
• 重原子数：
  28
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  11,14-Dibromo-phenanthro[3,4-c]phenanthrene 在 正丁基锂 、 氯化亚砜 作用下， 反应 13.5h， 生成 Hexahelicene-2,15-dicarbonyl chloride
  参考文献：
  名称：

  Synthesis of Conjugated Helical Acetylene-Bridged Polymers and Cyclophanes

  摘要：

  Pd(0)-catalyzed reactions of 2,15-diethynyl[6]helicene with derivatives of p- and o-diiodobenzene give, respectively, polymers 4 and cyclophanes 5, in which helicenes are linked by diethynylbenzenes. Both are very soluble in many common solvents. The molar rotation of polymer 4 is greater than that of monomeric analogue 12, and peaks in its UV and CD spectra at wavelengths greater than 350 nm are shifted to the red of those in 12. Cyclophane 5a, which contains two helicene rings, could be isolated from the reaction mixture in pure form. Its maxima in the UV and CD spectra are not shifted to the red of those of 12, most likely because the two helicene rings in 5a are twisted with respect to one another.

  DOI：

  10.1021/jo972101u
• 作为产物：
  描述：

  2,7-bis[2-(4-bromophenyl)ethinyl]naphthalene 在 碘 、 methyloxirane 作用下， 以 甲苯 为溶剂， 反应 5.25h， 以87%的产率得到11,14-Dibromo-phenanthro[3,4-c]phenanthrene
  参考文献：
  名称：

  莫比乌斯螺旋碳纳米环中的圆偏振发光**

  摘要：

  莫比乌斯螺旋烯纳米环：具有莫比乌斯拓扑结构的手性螺旋烯碳纳米环是通过将具有平面π电子共轭的立体[6]螺旋烯单元整合到径向共轭[7]环对亚苯基中而获得的。新的碳纳米环保留了环对亚苯基典型的有利光电特性，而[6]螺烯赋予其构型稳定性和手性特性，例如圆偏振发光。

  DOI：

  10.1002/anie.202208591

文献信息

• The First Helical-Chiral Phosphane Ligands: rac-[5]- and rac-[6]-Heliphos
  作者：Andreas Terfort、Helmar Görls、Henri Brunner

  DOI：10.1055/s-1997-1498

  日期：1997.1

  The syntheses of two helical, chiral phosphanes in their racemic forms are described. Their helicene backbone was built up using an improved photocyclization approach. The phosphorus functionalities were introduced in the last step. Up to now, separation of the enantiomers of the helicene phosphanes could be achieved analytically but not on a preparative scale.

  描述了两种螺旋型手性磷烷的合成过程，均为其消旋形式。它们的螺旋烯主链采用改进的光环化方法构建。磷功能团在最后一步引入。到目前为止，螺旋型磷烷的对映异构体可在分析层面上分离，但尚无法在制备规模上实现。
• First enantioselective catalysis using a helical diphosphane
  作者：Manfred T Reetz、Eckart W Beuttenmüller、Richard Goddard

  DOI：10.1016/s0040-4039(97)00562-5

  日期：1997.5

  The synthesis of 2,15-bis(diphenylphosphino)-hexahelicene (PHelix) in enantiomerically pure form and its use as a helical ligand for enantioselective rhodiumcatalyzed hydrogenation are described.

  描述了对映体纯形式的2,15-双（二苯基膦基）-己烯（PHelix）的合成及其作为对映选择性铑催化的氢化反应的螺旋配体的用途。
• Synthesis and chiral recognition of novel crown ethers incorporating helicene chiral centres
  作者：Masao Nakazaki、Koji Yamamoto、Tetsumi Ikeda、Tomohito Kitsuki、Yoshio Okamoto

  DOI：10.1039/c39830000787

  日期：——

  Two novel optically active crown ethers (7) and (14) incorporating helicene molecular frameworks were prepared, and their chiral recognition properties were examined to show that (M)-(–)-(7) and (M)-(–)-(14) had opposite chiral recognition for the transport of methyl phenylglycinate or 1-phenylethylamine.

  制备了两种新的旋光活性冠醚（7）和（14）并结合了螺旋烯分子骨架，并对其手性识别性能进行了研究，结果表明（M）-（-）-（7）和（M）-（-）- （14）对苯基甘氨酸甲酯或1-苯基乙胺的转运具有相反的手性识别。
• Circularly Polarized Luminescence of [6]Helicenes through Excited‐State Intramolecular Proton Transfer
  作者：Dominik Göbel、Sandra Míguez‐Lago、Maria Jose Ruedas‐Rama、Angel Orte、Araceli G. Campaña、Michal Juríček

  DOI：10.1002/hlca.202100221

  日期：2022.4

  hydroxylated [6]helicene were studied in parallel with a non-hydroxylated [6]helicene control compound, revealing that the presence of a chiral [6]helicene unit results in a strong CPL response and the presence of the ESIPT units in a considerable red shift. The red-shifted emission along with the outstanding glum (≈10−2) and a large Stokes shift makes the doubly hydroxylated [6]helicene a promising candidate

  我们提出了将圆偏振发光 (CPL) 和激发态分子内质子转移 (ESIPT) 特征结合到单个分子中的概念，作为生成高性能 ESIPT 基 CPL 材料的策略。为此，使用双Suzuki-Miyaura反应和双 C(sp 2 )-H 羟基化方法合成了带有两个 ESIPT 结构单元的 [6] 螺旋烯。双羟基化 [6] 螺烯的光物理性质与非羟基化 [6] 螺烯对照化合物平行研究，表明手性 [6] 螺烯单元的存在导致强烈的 CPL 响应和ESIPT 单位发生相当大的红移。红移发射以及出色的亮度（≈10 -2）和大的斯托克斯位移使双羟基化的[6]螺旋烯成为用于光电子学的有希望的候选者。
• Chiral Self‐Discrimination and Guest Recognition in Helicene‐Based Coordination Cages
  作者：Thorben R. Schulte、Julian J. Holstein、Guido H. Clever

  DOI：10.1002/anie.201812926

  日期：2019.4.16

  reaction control in biological systems. Supramolecular self‐assembly gives access to artificial mimics with tunable sizes and properties. Herein, a new family of [Pd2L4] coordination cages based on a chiral [6]helicene backbone is introduced. A racemic mixture of the bis‐monodentate pyridyl ligand L1 selectively assembles with PdII cations under chiral self‐discrimination to an achiral meso cage, cis‐[Pd2L1P2L1M2]

  手性纳米级禁闭对于生物系统中的对映选择性识别和反应控制起着重要作用。超分子自组装可访问具有可调大小和特性的人工模拟物。在此，介绍了一种基于手性[6]螺旋烯骨架的[Pd 2 L 4 ]配位笼的新家族。双单齿吡啶基配体L 1的外消旋混合物在手性自识别下与Pd II阳离子选择性组装成非手性介观笼，顺式[Pd 2 L 1 P 2 L 1 M 2 ]。对映体L 1形成同手性笼[Pd 2 L 1 P / M 4 ]。较长的衍生物L 2形成具有较大空腔的手性笼[Pd 2 L 2 P / M 4 ]，它们结合具有不同亲和力的手性客体的旋光异构体。由于其独特的手性，该笼子可以区分不同长度的非手性客体，因为发现它们在螺旋形螺距的调节下挤压或拉长了空腔。CD光谱结果得到离子迁移质谱的支持。