tert-butyl 2-(1,7,7-trimethylbicyclo[2.2.1]heptan-2-ylidene)hydrazinecarboxylate | 1436393-18-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: tert-butyl 2-(1,7,7-trimethylbicyclo[2.2.1]heptan-2-ylidene)hydrazinecarboxylate
• CAS: 1436393-18-8
• 化学式: C₁₅H₂₆N₂O₂
• 分子量: 266.384
• InChiKey: XVMNNVQZLRQYIP-BMIGLBTASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.71
• 重原子数：
  19.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  50.69
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  norbornene 、 tert-butyl 2-(1,7,7-trimethylbicyclo[2.2.1]heptan-2-ylidene)hydrazinecarboxylate 在 三氟甲苯 作用下， 反应 3.0h， 以80%的产率得到(±)-exo-2-(1,7,7-trimethylbicyclo[2.2.1]heptan-2-ylidene)-4-oxo-2,3-diazatricyclo[4,3,16,9,0]-decane-2-ium-3-ide
  参考文献：
  名称：

  Synthesis and Reactivity of Unsymmetrical Azomethine Imines Formed Using Alkene Aminocarbonylation

  摘要：

  Complex cyclic azomethine imines possessing a beta-aminocarbonyl motif can be accessed readily from simple alkenes and hydrazones. This alkene aminocarbonylation approach allows formation of ketone-derived azomethine imines of unprecedented complexity. Since unsymmetrical hydrazones are used, two stereoisomers are formed: the reactivity of chiral derivatives is explored in both intra- and intermolecular systems.

  DOI：

  10.1021/ol400542b
• 作为产物：
  描述：

  白樟油 、 phenyl hydrazinecarboxylate 在 溶剂黄146 作用下， 以 甲醇 为溶剂， 以57%的产率得到tert-butyl 2-(1,7,7-trimethylbicyclo[2.2.1]heptan-2-ylidene)hydrazinecarboxylate
  参考文献：
  名称：

  Synthesis and Reactivity of Unsymmetrical Azomethine Imines Formed Using Alkene Aminocarbonylation

  摘要：

  Complex cyclic azomethine imines possessing a beta-aminocarbonyl motif can be accessed readily from simple alkenes and hydrazones. This alkene aminocarbonylation approach allows formation of ketone-derived azomethine imines of unprecedented complexity. Since unsymmetrical hydrazones are used, two stereoisomers are formed: the reactivity of chiral derivatives is explored in both intra- and intermolecular systems.

  DOI：

  10.1021/ol400542b

文献信息

• Intermolecular Aminocarbonylation of Alkenes using Concerted Cycloadditions of Iminoisocyanates
  作者：Amanda Bongers、Christian Clavette、Wei Gan、Serge I. Gorelsky、Lyanne Betit、Kaitlyn Lavergne、Thomas Markiewicz、Patrick J. Moon、Nicolas Das Neves、Nimrat K. Obhi、Amy B. Toderian、André M. Beauchemin

  DOI：10.1021/acs.joc.6b02713

  日期：2017.1.20

  that the LUMO of the iminoisocyanate is reacting with the HOMO of the alkene. Computational and experimental results support a concerted asynchronous [3 + 2] cycloaddition involving an iminoisocyanate, which was observed for the first time by FTIR under the reaction conditions. The products of this reaction are complex azomethine imines, which are precursors to valuable β-amino carbonyl compounds such

  烯烃的氨基羰基化是访问仍未开发的β-氨基羰基基序的有效方法。在此，提出了亚氨基异氰酸酯与烯烃的分子间氨基羰基化反应性的发展。这包括发现芴酮衍生的试剂，该试剂对许多烯烃类别均有效，并有助于衍生化。富电子的底物最具反应性，这表明亚氨基异氰酸酯的LUMO与烯烃的HOMO反应。计算和实验结果支持涉及亚氨基异氰酸酯的协同异步[3 + 2]环加成反应，这是在反应条件下首次通过FTIR观察到的。该反应的产物是复杂的甲亚胺亚胺，它们是有价值的β-氨基羰基化合物（例如β-氨基酰胺和酯，吡唑啉酮和双环吡唑烷酮）的前体。通过对映选择性还原动力学拆分偶氮甲亚胺（s = 13–43）允许获得对映体富集的产品。总的来说，这项工作提供了一种将烯烃转化为β-氨基羰基化合物的新工具。