(E)-N-((E)-2-methylbut-2-en-1-ylidene)-1-phenylmethanamine

• 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-((E)-2-methylbut-2-en-1-ylidene)-1-phenylmethanamine
• 化学式: C₁₂H₁₅N
• 分子量: 173.258
• InChiKey: HCHTZDKUUGZROI-IKVDTSIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.22
• 重原子数：
  13.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  12.36
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  3-己炔 、 (E)-N-((E)-2-methylbut-2-en-1-ylidene)-1-phenylmethanamine 在 [RhCl(coe)2]2 作用下， 以 甲苯 为溶剂， 反应 6.0h， 以88%的产率得到N-benzyl-2,3-diethyl-4,5-dimethyl-1,2-dihydropyridine
  参考文献：
  名称：

  Synthesis of Dihydropyridines and Pyridines from Imines and Alkynes via C−H Activation

  摘要：

  A convenient one-pot C-H alkenylation/electrocyclization/aromatization sequence has been developed for the synthesis of highly substituted pyridine derivatives from alkynes and alpha,beta-unsaturated N-benzyl aldimines and ketimines that proceeds through dihydropyridine intermediates. A new class of ligands for C-H activation was developed, providing broader scope for the alkenylation step than could be achieved with previously reported ligands. Substantial information was obtained about the mechanism of the reaction. This included the isolation of a C-H activated complex and its structure determination by X-ray analysis; in addition, kinetic simulations using the Copasi software were employed to determine rate constants for this transformation, implicating facile C-H oxidative addition and slow reductive elimination steps.

  DOI：

  10.1021/ja7104784
• 作为产物：
  描述：

  反式-2-甲基-2-丁烯醛 、 苄胺 在 molecular sieve 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 生成 (E)-N-((E)-2-methylbut-2-en-1-ylidene)-1-phenylmethanamine
  参考文献：
  名称：

  Reactions of 1-Aza-1,3-butadienes. An Expedient Synthesis of Unsymmetrically Substituted N-Benzyl-1,4-dihydropyridines and N-Benzyl-1,4-dihydronicotinamides.

  摘要：

  DOI：

  10.3891/acta.chem.scand.51-0348

文献信息

• Stereoselective Alkylation of α,β-Unsaturated Imines via C−H Bond Activation
  作者：Denise A. Colby、Robert G. Bergman、Jonathan A. Ellman

  DOI：10.1021/ja0584931

  日期：2006.5.1

  alkylation of α,β-unsaturated imines via C−H activation followed by imine hydrolysis produces tri- and tetrasubstituted α,β-unsaturated aldehydes. In the presence of a rhodium catalyst, α,β-unsaturated N-benzyl imines derived from methacrolein, crotonaldehyde, and tiglic aldehyde undergo directed C−H activation at the β-position and react with terminal alkenes and alkynes to form the tri- and tetrasubstituted

  α,β-不饱和亚胺通过 CH 活化进行立体选择性烷基化，然后亚胺水解产生三和四取代的 α,β-不饱和醛。在铑催化剂存在下，衍生自异丁烯醛、巴豆醛和tiglic 醛的α,β-不饱和N-苄基亚胺在β-位进行定向C-H 活化，并与末端烯烃和炔烃反应形成三-和具有非常高立体选择性的四取代 α,β-不饱和亚胺。水解以提供 α,β-不饱和醛可以在保持β-烷基化亚胺产物立体化学的仔细控制的条件下进行。或者，对于甲基丙烯醛的 N-苄基亚胺的 β-烷基化产物，可以在提供完全异构化为 E 异构体的条件下进行水解。
• Regio- and Diastereoselective Synthesis of Highly Substituted, Oxygenated Piperidines from Tetrahydropyridines
  作者：Shuming Chen、Brandon Q. Mercado、Robert G. Bergman、Jonathan A. Ellman

  DOI：10.1021/acs.joc.5b00816

  日期：2015.7.2

  Diastereoselective epoxidation and regioselective ring-opening methods were developed for the synthesis of densely substituted, oxygenated piperidines from two classes of tetrahydropyridines with distinct stereochemical displays of functionalities. A new and practical in situ prepared epoxidation reagent was developed for the diastereoselective epoxidation of one class of sterically hindered tetrahydropyridines

  开发了非对映选择性环氧化和区域选择性开环方法，用于从两类具有不同立体化学功能的四氢吡啶合成密集取代的氧化哌啶。开发了一种新型实用的原位制备环氧化试剂，用于一类空间位阻四氢吡啶的非对映选择性环氧化。新型双功能环氧化试剂，2-过氧碳-3,4,5,6-四氟苯甲酸，旨在结合高反应性的过羧酸和侧链羧酸基团，通过氢键与氨基成功地克服空间效应并直接环氧化发生在四氢吡啶的受阻较多的面上。环氧化物与水、醇和 HF 的亲核开环以高区域选择性进行，得到具有相邻四取代碳的哌啶醇产物。
• Synthesis of Dihydropyridines and Pyridines from Imines and Alkynes via C−H Activation
  作者：Denise A. Colby、Robert G. Bergman、Jonathan A. Ellman

  DOI：10.1021/ja7104784

  日期：2008.3.1

  A convenient one-pot C-H alkenylation/electrocyclization/aromatization sequence has been developed for the synthesis of highly substituted pyridine derivatives from alkynes and alpha,beta-unsaturated N-benzyl aldimines and ketimines that proceeds through dihydropyridine intermediates. A new class of ligands for C-H activation was developed, providing broader scope for the alkenylation step than could be achieved with previously reported ligands. Substantial information was obtained about the mechanism of the reaction. This included the isolation of a C-H activated complex and its structure determination by X-ray analysis; in addition, kinetic simulations using the Copasi software were employed to determine rate constants for this transformation, implicating facile C-H oxidative addition and slow reductive elimination steps.
• Reactions of 1-Aza-1,3-butadienes. An Expedient Synthesis of Unsymmetrically Substituted N-Benzyl-1,4-dihydropyridines and N-Benzyl-1,4-dihydronicotinamides.
  作者：Jon K. F. Giersson、Jonina F. Johannesdóttir、Johannes Reynisson、Juhani Huuskonen、Kari Rissanen、Wenjun Shi、Stenbjörn Styring、Cecilia Tommos、Kurt Warncke、Bryan R. Wood

  DOI：10.3891/acta.chem.scand.51-0348

  日期：——