7-(2-methylbut-3-en-2-yl)-7-azabicyclo[4.1.0]heptane

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氮杂环庚烷
• 英文名称: 7-(2-methylbut-3-en-2-yl)-7-azabicyclo[4.1.0]heptane
• 英文别名: 7-(1,1-dimethylallyl)-7-azabicyclo[4.1.0]heptane
• 化学式: C₁₁H₁₉N
• 分子量: 165.279
• InChiKey: TYTGHUHIFCEEKO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  异戊烯醇 在 bis(η3-allyl-μ-chloropalladium(II)) 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 11.0h， 生成 7-(2-methylbut-3-en-2-yl)-7-azabicyclo[4.1.0]heptane
  参考文献：
  名称：

  Unusual Selectivity of Unprotected Aziridines in Palladium-Catalyzed Allylic Amination Enables Facile Preparation of Branched Aziridines

  摘要：

  Functionalized branched aziridines can be prepared in high yields and with high levels of regioselectivity using unprotected aziridines as nitrogen sources in palladium-catalyzed allylic amination. High levels of enantioselectivity can be achieved with BINAP on palladium. This methodology allows for strategic placement of an aziridine-containing fragment within a complex molecule environment for further elaboration.

  DOI：

  10.1021/ja049242f

文献信息

• Stereoselective Isomerisation of N-Allyl Aziridines into Geometrically StableZ Enamines by Using Rhodium Hydride Catalysis
  作者：Derek S. Tsang、Sharon Yang、France-Aimée Alphonse、Andrei K. Yudin

  DOI：10.1002/chem.200701322

  日期：2008.1.18

  the most likely mechanism of isomerisation would involve a rhodium hydride addition/beta-hydride elimination sequence. We show that the observed selectivity cannot be adequately explained by this pathway and is more consistent with initial CH-activation followed by rearrangement to form a five-membered cyclometallated rhodium intermediate. This intermediate subsequently undergoes reductive elimination

  在氢化铑（I）催化剂的存在下，已知N-烯丙基叔胺异构化成E-烯胺。相反，我们最近发现N-烯丙基氮丙啶异构化形成Z烯胺。根据文献数据，最可能的异构化机理将涉及氢化铑加成/β-氢化物消除序列。我们表明，所观察到的选择性不能通过该途径充分解释，并且与初始CH活化及随后的重排形成五元环金属化铑中间体更为一致。该中间体随后经过还原消除形成CH键。所得的几何稳定的Z-烯胺是用于立体选择性合成的有用的结构单元。
• Unusual Selectivity of Unprotected Aziridines in Palladium-Catalyzed Allylic Amination Enables Facile Preparation of Branched Aziridines
  作者：Iain D. G. Watson、Sarah A. Styler、Andrei K. Yudin

  DOI：10.1021/ja049242f

  日期：2004.4.28

  Functionalized branched aziridines can be prepared in high yields and with high levels of regioselectivity using unprotected aziridines as nitrogen sources in palladium-catalyzed allylic amination. High levels of enantioselectivity can be achieved with BINAP on palladium. This methodology allows for strategic placement of an aziridine-containing fragment within a complex molecule environment for further elaboration.