4-([2.2]paracyclophanyl)-N-methylamine | 123439-13-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4-([2.2]paracyclophanyl)-N-methylamine
• 英文别名: N-methyl-(N-4-[2.2]paracyclophanyl)amine；4-N-methylamino<2.2>paracyclophane；methyl-(4-[2.2]paracyclophanyl)amine；N-methyltricyclo[8.2.2.24,7]hexadeca-1(13),4,6,10(14),11,15-hexaen-5-amine
• CAS: 123439-13-4；123439-29-2；123439-42-9
• 化学式: C₁₇H₁₉N
• 分子量: 237.345
• InChiKey: GLIABXUVCVHFSN-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：
  1
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-([2.2]paracyclophanyl)-N-methylamine 在 N-溴代丁二酰亚胺(NBS) 、 甲基溴化镁 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 生成 2-bromo-N-methyl-N-(5-tricyclo[8.2.2.24,7]hexadeca-1(13),4,6,10(14),11,15-hexaenyl)propanamide
  参考文献：
  名称：

  Pelter, Andrew; Kidwell, Huw; Crump, Roger A. N. C., Journal of the Chemical Society. Perkin transactions I, 1997, # 21, p. 3137 - 3139

  摘要：

  DOI：
• 作为产物：
  描述：

  tert-butyl N-methyl-N-(5-tricyclo[8.2.2.24,7]hexadeca-1(13),4,6,10(14),11,15-hexaenyl)carbamate 在 三氟乙酸 作用下， 以95%的产率得到4-([2.2]paracyclophanyl)-N-methylamine
  参考文献：
  名称：

  Pelter, Andrew; Kidwell, Huw; Crump, Roger A. N. C., Journal of the Chemical Society. Perkin transactions I, 1997, # 21, p. 3137 - 3139

  摘要：

  DOI：

文献信息

• Diastereoselective Hartwig–Buchwald Reaction of Chiral Amines withrac-[2.2]Paracyclophane Derivatives
  作者：Michael Kreis、Christian J. Friedmann、Stefan Bräse

  DOI：10.1002/chem.200500386

  日期：2005.12.9

  rac-4-bromo-[2.2]paracyclophane and rac-trifluoromethanesulfonic acid (4-[2.2]paracyclophane) ester was performed with high diastereoselectivities. Kinetic racemic resolution of the starting materials was achieved, providing a rapid access to enantiomerically enriched 4-bromo-[2.2]paracyclophane and the corresponding enantiomerically pure [2.2]paracyclophane amines. Additionally, the first reaction of a secondary

  Hartwig-Buchwald将多种手性胺加至rac-4-溴-[2.2]对环环烷和rac-三氟甲磺酸（4- [2.2]对环环烷）酯中，具有很高的非对映选择性。达到了原料的动力学外消旋拆分，可以快速获得对映体富集的4-溴-[2.2]对环环糊精和相应的对映体纯的[2.2]对环环糊精胺。另外，实现了仲胺与[2.2]对环环烷卤化物的第一反应。
• Synthesis of novel planar-chiral [2.2]paracyclophane derivatives as potential ligands for asymmetric catalysis
  作者：Michael Kreis、Martin Nieger、Stefan Bräse

  DOI：10.1016/j.jorganchem.2005.10.031

  日期：2006.5

  The synthesis of a variety of new 4,5-disubstituted [2.2]paracyclophane derivatives has been achieved employing different cross-coupling reactions. By this methodology, a heteroatom-variation of successful catalyst ligands was achieved, giving rise to a modular ligand system. The X-ray structure of 4-hydroxy-5-(1′-hydroxy-1′-phenylethyl)-[2.2]paracyclophane was determined to elucidate the configuration

  已经使用不同的交叉偶联反应实现了多种新的4，5-二取代的[2.2]对环环烷衍生物的合成。通过这种方法，成功的催化剂配体实现了杂原子变异，从而产生了模块化的配体体系。确定4-羟基-5-（1'-羟基-1'-苯乙基）-[2.2]对环烷的X射线结构以阐明其构型。另外，实现了平面和中心手性的4-（[2.2]对环苯甲酰基）乙胺的非对映选择性合成，因此得到了平面和中心手性的苯基乙胺类似物。
• Novel [2.2]paracyclophane derivatives via charge-transfer complexation
  作者：Ashraf A. Aly、Alaa A. Hassan、Aboul-Fetouh E. Mourad

  DOI：10.1139/v93-231

  日期：1993.11.1

  The transannular electronic interactions in [2.2]paracyclophanes affect the selectivity of the tricyanovinylation reaction with tetracyanoethylene (TCNE). In addition to the normal N-tricyanovinyl product, 4-amino[2,2]paracyclophane reacts with TCNE to give oxaziridine derivatives. In the case of reaction with 4-N-methylamino[2.2]paracyclophane, the unusual N-tricyanovinylated product as well as 4

  [2.2] 对环芳中的跨环电子相互作用影响三氰基乙烯基化反应与四氰基乙烯 (TCNE) 的选择性。除了正常的 N-三氰基乙烯基产物外，4-氨基 [2,2] 对环烷与 TCNE 反应生成恶氮丙啶衍生物。在与 4-N-甲氨基[2.2] 对环烷反应的情况下，分离出不寻常的 N-三氰基乙烯基化产物以及 4-(N-甲腈-N-甲基) 氨基[2.2] 对环烷。2,3-二氯-5,6-二氰基-1,4-苯醌 (DDQ) 与 4-氨基[2.2] 对环芳烷反应生成 2-氰基-3-(4-[2.2] 对环芳基)氨基-5,6-二氯-1,4-苯醌。
• Cycloadditions of α-(4-[2.2]paracyclophanyl)-N-methyl nitrone
  作者：Ashraf A. Aly、Henning Hopf、Peter G. Jones、Ina Dix

  DOI：10.1016/j.tet.2006.02.047

  日期：2006.5

  Cycloadditions of the newly synthesized α-(4-[2.2]paracyclophanyl)-N-methyl nitrone (9) with selected dipolarophiles such as phenyl isocyanate (10), styrene (13), dimethyl acetylenedicarboxylate (15) and methylene sulfene (17) are reported. Two isolated diastereomeric oxadiazolones 11 and 12 are obtained by the reaction of 9 with 10, whereas the reaction of 9 with either 13 and/or 15 gives only one

  新合成的α-（4- [2.2]对环苯甲酰基）-N-甲基硝酮（9）与选定的双极性亲和剂，如异氰酸苯酯（10），苯乙烯（13），乙炔二羧酸二甲酯（15）和亚甲基亚砜（17）的环加成反应被报道。通过9与10的反应获得两个分离的非对映异构的恶二唑酮11和12，而9与13和/或15的反应仅得到一个非对映异构体异恶唑14和/或16。通过9与17的反应获得4-（[2.2] Paracylophanyl）-N-甲胺（20）。化合物的结构9，11和14是由X射线结构分析分配。
• 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.