(E)-N-(1-(3-methoxyphenyl)ethylidene)aniline | 1431475-36-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (E)-N-(1-(3-methoxyphenyl)ethylidene)aniline
• CAS: 1431475-36-3
• 化学式: C₁₅H₁₅NO
• 分子量: 225.29
• InChiKey: XWKUOVKNYOIOMS-FOWTUZBSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.84
• 重原子数：
  17.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  21.59
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (E)-N-(1-(3-methoxyphenyl)ethylidene)aniline 在 氢气 、 (E)-4,4-dimethyl-1-(2-methyl-4-(1-(phenylimino)ethyl)phenyl)piperidine-2,6-dione 、 [Ir(MaxPHOX)(cod)]BArF 作用下， 以 二氯甲烷 为溶剂， 以98%的产率得到
  参考文献：
  名称：

  Cyclometallated Imides as Templates for the H‐Bond Directed Iridium‐Catalyzed Asymmetric Hydrogenation of N‐Methyl, N‐Alkyl and N‐Aryl Imines

  摘要：

  A combined computational and experimental approach allowed us to develop the most selective catalysts for the direct hydrogenation of N‐methyl and N‐alkyl imines described to date. Iridium catalysts with a cyclometallated cyclic imide group provide selectivity of up to 99% enantiomeric excess. Computational studies show that the selectivity results from the combined effect of H‐bonding of the imide C=O with the substrate iminium ion and a stabilizing π‐π interaction with the cyclometallated ligand. The cyclometallated ligand thus exhibits a unique mode of action, serving as a template for the H‐bond directed approach of the substrate which results in enhanced selectivity. The catalyst (2) has been synthesized and isolated as a crystalline air‐stable solid. X‐ray analysis of 2 confirmed the structure of the catalyst and the correct position of the imide C=O groups to engage in an H‐bond with the substrate. 19F‐NMR real‐time monitoring showed the hydrogenation of N‐methyl imines catalyzed by 2 is very fast, with a TOF of approx. 3500 h‐1.

  DOI：

  10.1002/anie.202404955
• 作为产物：
  描述：

  苯胺 、 3-甲氧基苯乙酮 在 四氯化钛 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 12.7h， 生成 (E)-N-(1-(3-methoxyphenyl)ethylidene)aniline
  参考文献：
  名称：

  手性二烯作为硼烷催化亚胺无金属不对称氢化的“配体”

  摘要：

  本文描述了使用手性二烯作为“配体”对亚胺进行高度对映选择性的无金属氢化，通过原位硼氢化反应生成具有 HB(C6F5)2 的催化剂，以提供各种手性胺，其 ee 高达 89%，从而提供开发用于不对称氢化的新型手性受阻路易斯对的实用策略。

  DOI：

  10.1021/ja4025808

文献信息

• P-Stereogenic and Non-P-Stereogenic Ir–MaxPHOX in the Asymmetric Hydrogenation of <i>N</i>-Aryl Imines. Isolation and X-ray Analysis of Imine Iridacycles
  作者：Ernest Salomó、Pep Rojo、Pol Hernández-Lladó、Antoni Riera、Xavier Verdaguer

  DOI：10.1021/acs.joc.8b00361

  日期：2018.4.20

  A small library of Ir–MaxPHOX catalysts has been applied to the asymmetric hydrogenation of N-aryl imines. A structure–activity analysis of the three-chiral-center MaxPHOX ligand has been performed. Using complex 1b, the hydrogenation of N-aryl imines took place with up to 96% enantiomeric excess at atmospheric pressure of hydrogen and low temperature. The impact of the stereochemical information at

  一个小的Ir–MaxPHOX催化剂库已用于N-芳基亚胺的不对称氢化。进行了三个手性中心MaxPHOX配体的结构活性分析。使用配合物1b进行N的氢化在氢气的大气压和低温下，发生了最多达96％对映体过量的芳基亚胺。就选择性而言，在磷中心的立体化学信息的影响较小，而对于催化剂活性而言，其影响较大。还合成和测试了MaxPHOX的非P-立体生成类似物，但它们具有较低的选择性。可以通过考虑实际的催化剂是原位形成的环金属化的亚胺配合物来解释观察到的选择性。[IrHCl（MaxPHOX）（亚胺）]配合物9和10合成并通过X射线晶体学表征。这些络合物通过氯化物提取，为活性催化物质提供了相同水平的选择性。最后，还研究了抗衡离子对催化剂性能的影响。
• Dehydrogenative N-Incorporation: A Direct Approach to Quinoxaline<i>N</i>-Oxides under Mild Conditions
  作者：Feng Chen、Xiaoqiang Huang、Xinyao Li、Tao Shen、Miancheng Zou、Ning Jiao

  DOI：10.1002/anie.201406479

  日期：2014.9.22

  An efficient method for the synthesis of quinoxaline N‐oxides proceeds by the dehydrogenative N‐incorporation of simple imines by C(sp2)H and C(sp3)H bond functionalization. The overall transformation involves the cleavage of three CH bonds. The reaction is easily handled and proceeds under mild conditions. Simple and readily available tert‐butyl nitrite (TBN) was employed as the NO source.

  一种有效的合成喹喔啉N-氧化物的方法是通过C（sp 2）H和C（sp 3）H键功能化使简单的亚胺脱氢N-并入。整体转化涉及三个CH键的裂解。该反应易于处理并在温和条件下进行。简单易得的亚硝酸叔丁酯（TBN）被用作NO源。
• Hydrogenation and Transfer Hydrogenation Promoted by Tethered Ru−S Complexes: From Cooperative Dihydrogen Activation to Hydride Abstraction/Proton Release from Dihydrogen Surrogates
  作者：Alice Lefranc、Zheng-Wang Qu、Stefan Grimme、Martin Oestreich

  DOI：10.1002/chem.201600386

  日期：2016.7.11

  well as with a representative Hantzsch ester dihydrogen surrogate, are reported. Both processes are catalyzed by tethered Ru−S complexes but differ in the activation mode of the dihydrogen source: cooperative activation of the H−H bond at the Ru−S bond leads to the corresponding Ru−H complex and protonation of the sulfur atom, whereas the same cationic Ru−S catalyst abstracts a hydride from a donor‐substituted

  据报道，亚胺用环己-1,4-二烯以及具有代表性的汉茨酯二氢替代物进行加氢和转移加氢。这两个过程都是通过束缚的Ru-S络合物催化的，但是在二氢源的活化方式上有所不同：在Ru-S键上H-H键的协同活化会导致相应的Ru-H络合物和硫原子的质子化，而相同的阳离子Ru-S催化剂从供体取代的环己-1,4-二烯中提取氢化物，形成中性Ru-H络合物和低能Wheland中间体。然后，在亚胺底物上进行一系列的质子和氢化物转移，生成胺。对反应路径进行了计算分析，建立的机理图与实验结果吻合。