(2R,3R,12R,13R,22R,23R)-1,4,11,14,21,24-hexaaza-(2,3:12,13:22,23)-tributano-(6,9:16,19:26,29)-trietheno-(1H,2H,3H,4H,5H,10H,11H,12H,13H,14H,15H,20H,21H,22H,23H,24H,25H,30H)-octadecahydro-(30)-annulene | 302792-02-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (2R,3R,12R,13R,22R,23R)-1,4,11,14,21,24-hexaaza-(2,3:12,13:22,23)-tributano-(6,9:16,19:26,29)-trietheno-(1H,2H,3H,4H,5H,10H,11H,12H,13H,14H,15H,20H,21H,22H,23H,24H,25H,30H)-octadecahydro-(30)-annulene
• 英文别名: (4R,9R,18R,23R,32R,37R)-3,10,17,24,31,38-hexazaheptacyclo[38.2.2.212,15.226,29.04,9.018,23.032,37]octatetraconta-1(43),12,14,26(46),27,29(45),40(44),41,47-nonaene
• CAS: 302792-02-5
• 化学式: C₄₂H₆₀N₆
• 分子量: 648.979
• InChiKey: WXGWBHHIOPJDOA-GIEDQAFWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  48
• 可旋转键数：
  0
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  72.2
• 氢给体数：
  6
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2R,3R,12R,13R,22R,23R)-1,4,11,14,21,24-hexaaza-(2,3:12,13:22,23)-tributano-(6,9:16,19:26,29)-trietheno-(1H,2H,3H,4H,5H,10H,11H,12H,13H,14H,15H,20H,21H,22H,23H,24H,25H,30H)-octadecahydro-(30)-annulene 在 ammonium tetrafluoroborate 、 原甲酸三乙酯 作用下， 以 5,5-dimethyl-1,3-cyclohexadiene 为溶剂， 反应 4.0h， 以68%的产率得到
  参考文献：
  名称：

  一个新的手性N-杂环卡宾银（I）圆柱：合成，晶体结构和催化性能。

  摘要：

  通过自组装制备了一种新的手性环状三咪唑啉盐及其手性N-杂环卡宾三银圆柱状笼，具有对几种席夫碱化合物进行氰基硅烷化反应的尺寸选择催化性能。

  DOI：

  10.1039/c000793e
• 作为产物：
  描述：

  (2R,3R,12R,13R,22R,23R)-1,4,11,14,21,24-hexaaza-(2,3:12,13:22,23)tributeno-(6,9:16,19:26,29)trietheno-2H,3H,12H,22H,23H-(30)-annulene 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 12.0h， 以65%的产率得到(2R,3R,12R,13R,22R,23R)-1,4,11,14,21,24-hexaaza-(2,3:12,13:22,23)-tributano-(6,9:16,19:26,29)-trietheno-(1H,2H,3H,4H,5H,10H,11H,12H,13H,14H,15H,20H,21H,22H,23H,24H,25H,30H)-octadecahydro-(30)-annulene
  参考文献：
  名称：

  一个新的手性N-杂环卡宾银（I）圆柱：合成，晶体结构和催化性能。

  摘要：

  通过自组装制备了一种新的手性环状三咪唑啉盐及其手性N-杂环卡宾三银圆柱状笼，具有对几种席夫碱化合物进行氰基硅烷化反应的尺寸选择催化性能。

  DOI：

  10.1039/c000793e
• 作为试剂：
  描述：

  对氰基苯乙酮 在 二苯基硅烷 、 diethylzinc 、 (2R,3R,12R,13R,22R,23R)-1,4,11,14,21,24-hexaaza-(2,3:12,13:22,23)-tributano-(6,9:16,19:26,29)-trietheno-(1H,2H,3H,4H,5H,10H,11H,12H,13H,14H,15H,20H,21H,22H,23H,24H,25H,30H)-octadecahydro-(30)-annulene 、 sodium hydroxide 作用下， 以 正己烷 、 甲苯 、 甲醇 为溶剂， 反应 25.0h， 生成 (S)-1-(4-氰基苯基)乙醇 、 (R)-1-(4-氰基苯基)乙醇
  参考文献：
  名称：

  锌-大环寡胺配合物催化的酮的便捷对映选择性氢化硅烷化

  摘要：

  Abstractmagnified imageChiral macrocyclic tetra‐ and hexamine macrocycles derived from trans‐1,2‐diaminocyclohexane (DACH) in complexes with diethylzinc efficiently catalyze the asymmetric hydrosilylation of aryl alkyl ketones with enantiomeric excess of the product up to 89%. The cyclic structure of the trianglamine ligand increases the enantioselectivity of the reaction, in comparison to the catalysis with the acyclic N,N′‐dibenzyl‐DACH ligand. Density functional theory (DFT) computations on the structures of ligand‐zinc complexes and on the structures of these complexes with a coordinated acetophenone molecule allow us to rationalize the direction of the asymmetric induction of the hydrosilylation reaction as well as the superiority of the cyclic ligand compared to the acyclic one. This is the first example of asymmetric catalysis for the hydrosilylation reaction of ketones with the use of a readily available, inexpensive, and reusable macrocyclic trianglamine ligand.

  DOI：

  10.1002/adsc.200800801

文献信息

• Attachment of trianglamines to silicon wafers, chiral recognition by chemical force microscopy
  作者：Jiri Hlinka、Jana Hodacova、Laurence Raehm、Michel Granier、Michel Ramonda、Jean-Olivier Durand

  DOI：10.1016/j.crci.2010.01.004

  日期：2010.4

  Résumé The chemical attachment of enantiomerically pure trianglamines to silicon wafers through isocyanate functions was performed. The self-assembled monolayer was analyzed by ATR-FTIR, ellipsometry, AFM, contact angle measurements. An AFM tip was functionalized by enantiomerically pure trianglamine using the same pathway. Chemical force microscopy showed chiral recognition between the functionalized tip and the functionalized wafer.

  简历 通过异氰酸酯功能团，实现了纯手性三联胺与硅晶片的化学键合。通过ATR-FTIR、椭偏仪、AFM和接触角测量分析了自组装单层膜。使用相同路径，将AFM针尖功能化为纯手性三联胺。化学力显微镜显示了功能化针尖与功能化晶片之间的手性识别。
• Stereoselective synthesis of ring C-hexasubstituted trianglamines
  作者：Diego Savoia、Andrea Gualandi、Helen Stoeckli-Evans

  DOI：10.1039/c004873a

  日期：——

  The addition of organolithium reagents to the trianglimine derived from (R,R)-1,2-diaminocyclohexane and terephthalaldehyde gave the corresponding trianglamine with complete stereocontrol and the R configuration of all six newly formed stereocenters. The structure of the hexaphenyl-substituted macrocyle was determined by X-ray crystallographic study. The new trianglamines were tested as ligands in enantioselective catalytic reactions.

  将有机锂试剂加入由(R,R)-1,2-二氨基环己烯和对苯二甲醛衍生的三氨基宁，得到了相应的三氨基宁，所有六个新形成的立体中心均具完全的立体选择性，且均为R构型。通过X射线晶体学研究确定了六苯基取代的巨环的结构。新的三氨基宁作为配体在对映选择性催化反应中进行了测试。
• Self-assembly of achiral and chiral macrocyclic ligands: synthesis, protonation constants, conformation and asymmetric catalysis
  作者：Jian Gao、Arthur E. Martell

  DOI：10.1039/b303678m

  日期：——

  determine the protonation constants of the ligands. UV-vis spectrophotometric titration was employed to investigate the coordination and conformational properties of the chiral ligand (L2). Direct enantioselective aldol reaction has been successfully performed using 4-nitrobenzaldehyde and acetone in the presence of the chiral macrocycle and its zinc(II) complexes as catalysts.

  分别由邻苯二甲醛与顺式和（1R，2R）-二氨基环己烷的[3 + 3]缩合直接合成新的30元非手性和手性聚氮杂大环配体L1和L2。通过电喷雾电离质谱（ESI-MS），1 H NMR，13 C NMR光谱和元素分析确认了三聚体大环结构。电位计用于确定配体的质子化常数。用紫外可见分光光度滴定法研究手性配体（L2）的配位和构象性质。在手性大环化合物及其锌（II）配合物为催化剂的情况下，使用4-硝基苯甲醛和丙酮已成功进行了直接对映选择性的羟醛反应。
• Synthesis, self-association and chiroselectivity of isotopically labeled trianglamine macrocycles in the ion trap mass spectrometer
  作者：Nikolai Kuhnert、Adam Le-Gresley、Daniel C. Nicolau、Ana Lopez-Periago

  DOI：10.1002/jlcr.1449

  日期：2007.11

  The synthesis and self-association of chiral isotopically labeled trianglamine macrocycles under electrospray mass spectrometer conditions in an ion trap are described. A moderate diastereoselectivity in the self-association process was observed providing a synthetic model system for the investigation of chiral self-association in the gas phase. The first non-covalently bound dimer exclusively bonded through aromatic–aromatic interactions was observed in the gas phase. Evidence for self-association in solution was observed by diffusion nuclear magnetic resonance spectroscopy. Copyright © 2007 John Wiley & Sons, Ltd.

  该研究描述了在离子阱电喷雾质谱条件下手性同位素标记的三苯胺大环的合成和自结合过程。在自结合过程中观察到了适度的非对映选择性，为研究气相中的手性自结合提供了一个合成模型系统。在气相中观察到了第一个完全通过芳香-芳香相互作用结合的非共价结合二聚体。通过扩散核磁共振光谱观察到了溶液中自结合的证据。Copyright © 2007 John Wiley & Sons, Ltd. All Rights Reserved.
• Trianglamines—Readily Prepared, Conformationally Flexible Inclusion-Forming Chiral Hexamines
  作者：Jacek Gawronski、Krystyna Gawronska、Jakub Grajewski、Marcin Kwit、Agnieszka Plutecka、Urszula Rychlewska

  DOI：10.1002/chem.200500887

  日期：2006.2.8

  Trianglamines, macrocyclic heteraphanes, were readily synthesised through a [3+3] cyclocondensation of (R,R)-1,2-diaminocyclohexane with terephthalaldehyde, followed by NaBH4 reduction and N-alkylation. The macrocyclic ring shows a remarkable ability to change its conformation, as a consequence of rotation about the C-N bonds or nitrogen inversion due to protonation or N-alkylation, as revealed by

  通过（R，R）-1,2-二氨基环己烷与对苯二醛的[3 + 3]环缩合，然后NaBH4还原和N-烷基化，可以轻松合成大环杂芳基三苯胺。大圆环显示出显着的改变其构象的能力，这是由于绕圆二色光谱，计算模型和X射线衍射分析所揭示的，由于绕CN键旋转或由于质子化或N-烷基化而引起的氮反转，导致其构象改变的能力。Trianglamine大环化合物的柔韧性使各种客体分子易于容纳，从而形成具有高度互穿结构的晶体包合物。