6,9,12,15,18,21-Hexaoxa-35,38-diazahexacyclo[24.8.4.22,5.222,25.029,37.032,36]dotetraconta-1(35),2(42),3,5(41),22(40),23,25(39),26(38),27,29(37),30,32(36),33-tridecaene | 90030-13-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 菲咯啉
• 英文名称: 6,9,12,15,18,21-Hexaoxa-35,38-diazahexacyclo[24.8.4.22,5.222,25.029,37.032,36]dotetraconta-1(35),2(42),3,5(41),22(40),23,25(39),26(38),27,29(37),30,32(36),33-tridecaene
• CAS: 90030-13-0
• 化学式: C₃₄H₃₄N₂O₆
• 分子量: 566.654
• InChiKey: BKWWFYJPTMXJGZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  42
• 可旋转键数：
  0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  81.2
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  6,9,12,15,18,21-Hexaoxa-35,38-diazahexacyclo[24.8.4.22,5.222,25.029,37.032,36]dotetraconta-1(35),2(42),3,5(41),22(40),23,25(39),26(38),27,29(37),30,32(36),33-tridecaene 以 二氯甲烷 、 乙腈 为溶剂， 反应 2.0h， 生成
  参考文献：
  名称：

  Cu-tethered macrocycle catalysts: Synthesis and size-selective CO2-fixation to propargylamines under ambient conditions

  摘要：

  A novel air-stable, Cu-tethered macrocycle catalyst possessing a large inner cavity was successfully synthesized, creating a unique supramolecular catalytic system. The catalyst was utilized in the CO2-fixation reaction to propargylamines. The reaction proceeded more efficiently compared to the conventional CuI catalyst under atmospheric CO2 condition. Notably, owing to its topological effect, the Cu-tethered macrocycle catalyst exhibited unique substrate size selectivity. (C) 2020 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2020.151966
• 作为产物：
  描述：

  4-溴苯酚 在 盐酸 、 四(三苯基膦)钯 、 正丁基锂 、 sodium carbonate 、 caesium carbonate 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 正己烷 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 107.92h， 生成 6,9,12,15,18,21-Hexaoxa-35,38-diazahexacyclo[24.8.4.22,5.222,25.029,37.032,36]dotetraconta-1(35),2(42),3,5(41),22(40),23,25(39),26(38),27,29(37),30,32(36),33-tridecaene
  参考文献：
  名称：

  Cu-tethered macrocycle catalysts: Synthesis and size-selective CO2-fixation to propargylamines under ambient conditions

  摘要：

  A novel air-stable, Cu-tethered macrocycle catalyst possessing a large inner cavity was successfully synthesized, creating a unique supramolecular catalytic system. The catalyst was utilized in the CO2-fixation reaction to propargylamines. The reaction proceeded more efficiently compared to the conventional CuI catalyst under atmospheric CO2 condition. Notably, owing to its topological effect, the Cu-tethered macrocycle catalyst exhibited unique substrate size selectivity. (C) 2020 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2020.151966

文献信息

• Synthesis of [2]-, [3]-, and [4]rotaxanes whose axis contains two bidentate and two tridentate chelates
  作者：Jean-Paul Collin、Stéphanie Durot、Jean-Pierre Sauvage、Yann Trolez

  DOI：10.1039/c1nj20213h

  日期：——

  A [3]rotaxane consisting of two 30-membered rings threaded by a symmetrical filament-like fragment was synthesized thanks to the copper(I)-template effect. The filament incorporates two tridentate coordinating units and two bidentate chelating groups. In addition to the [3]rotaxane, two homologous compounds were isolated in very significant yields: the corresponding [2]- and [4]-rotaxanes containing

  由于铜（I）-模板的作用，合成了由两个由对称的丝状片段穿线的30元环组成的[3]轮烷。该灯丝包含两个三齿配位单元和两个双齿螯合基团。除了[3]轮烷以外，还以非常高的收率分离出两种同源化合物：相应的[2]-和[4]-轮烷，其与[3]轮烷具有相同的线并分别包含一个或三个环。
• Use of Cleavable Coordinating Rings as Protective Groups in the Synthesis of a Rotaxane with an Axis that Incorporates More Chelating Groups Than Threaded Macrocycles
  作者：Antoine Joosten、Yann Trolez、Valérie Heitz、Jean-Pierre Sauvage

  DOI：10.1002/chem.201301717

  日期：2013.9.16

  methodology allowing preparation of a linear “unsaturated” [3]rotaxane consisting of an axis incorporating more coordination sites than threaded rings was developed. It was based on the preliminary synthesis of a “saturated” [5]rotaxane consisting of a four‐chelating site axis threaded through four macrocyclic components, two of them being cleavable rings incorporating a lactone function and the two

  开发了一种允许制备线性“不饱和” [3]轮烷的新方法，该轴由比螺纹环包含更多配位点的轴组成。它基于“饱和” [5]轮烷的初步合成，该轮烷由穿过四个大环组分的四个螯合位点轴组成，其中两个是带有内酯功能的可裂解环，另外两个是“安全的”非-可裂环。终止反应基于点击化学。随后，在碱性培养基中从[5]轮烷中裂解并除去两个含内酯的大环化合物，可定量获得所需的“不饱和” [3]轮烷。
• [3]Rotaxanes and [3]pseudorotaxanes with a rigid two-bidentate chelate axle threaded through two coordinating rings
  作者：Jean-Paul Collin、Jean-Pierre Sauvage、Yann Trolez、Kari Rissanen

  DOI：10.1039/b9nj00278b

  日期：——

  New [3]rotaxanes and [3]pseudorotaxanes have been synthesised using the “gathering and threading” effect of copper(I). By using click chemistry as the “stoppering” reaction, a good yield of the [3]rotaxane was obtained, either as a dicopper complex or as a metal-free compound after demetallation. The axle contains a central rigid aromatic block incorporating two bidentate chelates, and the threaded macrocycles are 30-membered rings. A model dicopper(I) [3]pseudorotaxane whose axle was end-functionalised by triisopropylsilyl groups could be crystallised and studied by X-ray diffraction. A particularly attractive structure was obtained showing a “slanted” geometry for the two rings and the axle, the two 1,10-phenanthroline units of the rings being almost parallel to one another but their respective mean planes being more than 7 Å apart.

  新的[3]轮烷和[3]假轮烷已通过铜(I)的“聚集和穿线”效应合成。使用点击化学作为“塞子”反应，获得了高产率的[3]轮烷，无论作为二铜配合物还是在脱金属后作为无金属化合物。轴包含一个中心刚性芳香块，结合了两个双齿螯合剂，而穿过的宏环是30元环。一个轴端功能化为三异丙基硅基的二铜(I)[3]假轮烷模型可以结晶并通过X射线衍射研究。获得了一个特别吸引人的结构，显示出两个环和轴的“倾斜”几何形状，两个1,10-菲咯啉单元几乎平行，但它们各自的平均平面相距超过7 Å。
• Unconventional Synthesis of a Cu^I Rotaxane with a Superacceptor Stopper: Ultrafast Excited-State Dynamics and Near-Infrared Luminescence
  作者：Yann Trolez、Aaron D. Finke、Fabio Silvestri、Filippo Monti、Barbara Ventura、Corinne Boudon、Jean-Paul Gisselbrecht、W. Bernd Schweizer、Jean-Pierre Sauvage、Nicola Armaroli、François Diederich

  DOI：10.1002/chem.201801161

  日期：2018.7.20

  processes is the lowest singlet state of the DCNQ moiety (S1), which exhibits strong charge‐transfer character and a lifetime of 0.4 ps. Its deactivation leads to population of another excited state with a lifetime of 1.3 ps, which can be the related triplet state (T1) or a vibrationally hot level (hot‐S0). Notably, S1 also shows stimulated fluorescence in the near‐infrared (NIR) region between 1100

  使用[2 + 2]环加成-逆电环化（CA-RE）反应接枝大体积的二氰基喹二甲烷（DCNQ）塞子制备了Cu I双-菲咯啉轮烷。通过电化学和光物理技术，与三种参考化合物（分别为单独的DCNQ衍生物，基于DCNQ的菲咯啉配体和缺少DCNQ部分的类似Cu I配合物）平行研究了电子性质。在所有包含DCNQ单元的系统中，最低的电子激发态都集中在其上，如TDDFT计算所建议的那样，单重态能级（S 1）位于约1.0 eV。因此，在配备DCNQ的轮烷中，Cu I的典型金属-配体电荷转移发光中心完全淬火。超快速瞬态吸收和发射研究表明，在轮烷中，光诱导过程的最终吸收是DCNQ部分（S 1）的最低单重态，它具有很强的电荷转移特性，寿命为0.4 ps。它的失活导致另一种激发态的填充，其寿命为1.3 ps，这可能是相关的三重态（T 1）或振动热能级（hot-S 0）。值得注意的是，S 1在1100至1500 nm之间
• Quantitative Formation of [2]Catenanes Using Copper(I) and Palladium(II) as Templating and Assembling Centers:  The Entwining Route and the Threading Approach
  作者：Christiane Dietrich-Buchecker、Benoît Colasson、Makoto Fujita、Akiko Hori、Neri Geum、Shigeru Sakamoto、Kentaro Yamaguchi、Jean-Pierre Sauvage

  DOI：10.1021/ja021370l

  日期：2003.5.1

  type of coordination catenanes incorporating Cu(I) and Pd(II) metal centers. The ligand designed here contains a phenanthroline core and pyridine sidearms (compound 1). Using this phenanthroline-pyridine conjugated ligand, two approaches were examined, which were shown to be surprisingly efficient for the catenane synthesis: the entwining route (entwining of two ligands around Cu(I) followed by Pd(II)

  过渡金属介导的模板和自组装已显示出合成互锁分子的强大潜力。这两种策略相结合，设计和制备了一种新型配位链烯，包括 Cu(I) 和 Pd(II) 金属中心。此处设计的配体包含菲咯啉核心和吡啶侧臂（化合物 1）。使用这种菲咯啉-吡啶共轭配体，研究了两种方法，它们被证明对链烷合成非常有效：缠绕途径（两个配体缠绕在 Cu(I) 周围，然后是 Pd(II) 剪切）和穿线法（Cu(I) 模板化的环状配体在无环配体上的穿线，然后是第二个环的 Pd(II) 剪切）。在前一种方法中，