N-(cyclopropylmethyl)-2-methylbut-3-en-2-amine | 960246-14-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N-(cyclopropylmethyl)-2-methylbut-3-en-2-amine
• CAS: 960246-14-4
• 化学式: C₉H₁₇N
• mdl: MFCD19227204
• 分子量: 139.241
• InChiKey: OGEHLGUOGPHBSE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.777
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  异戊烯醇 在 4-二甲氨基吡啶 、 bis(η3-allyl-μ-chloropalladium(II)) 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 亚磷酸三乙酯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 20.0h， 生成 N-(cyclopropylmethyl)-2-methylbut-3-en-2-amine
  参考文献：
  名称：

  Achieving Control over the Branched/Linear Selectivity in Palladium-Catalyzed Allylic Amination

  摘要：

  Palladium-catalyzed reaction of unsymmetrical allylic electrophiles with amines gives rise to regioisomeric allylic amines. We have found that linear products result from the thermodynamically controlled isomerization of the initially formed branched products. The isomerization is promoted by protic acid and active palladium catalyst. The use of base shuts down the isomerization pathway and allows for the preparation and isolation of branched allylic amines. Solvent plays a key role in achieving high kinetic regioselectivity and in controlling the rate of isomerization. The isomerization can be combined with ring-closing metathesis to afford the synthesis of exocyclic allylic amines from their endocyclic precursors.

  DOI：

  10.1021/jo3025253

文献信息

• Chasing the Proton Culprit from Palladium-Catalyzed Allylic Amination
  作者：Igor Dubovyk、Iain D. G. Watson、Andrei K. Yudin

  DOI：10.1021/ja076659n

  日期：2007.11.1

  We have found that the addition of base has a significant effect on palladium-catalyzed allylic amination. The long-standing problem of controlling the branched-to-linear ratio has been solved. In the presence of DBU and inexpensive, readily available ligands, palladium-catalyzed allylation proceeds under kinetic control, leading to high branched selectivity. Given the widespread utility of palladium-catalyzed allylic amination, we expect that these findings will be relevant in many areas ranging from asymmetric catalysis to target-oriented synthesis.
• Achieving Control over the Branched/Linear Selectivity in Palladium-Catalyzed Allylic Amination
  作者：Igor Dubovyk、Iain D. G. Watson、Andrei K. Yudin

  DOI：10.1021/jo3025253

  日期：2013.2.15

  Palladium-catalyzed reaction of unsymmetrical allylic electrophiles with amines gives rise to regioisomeric allylic amines. We have found that linear products result from the thermodynamically controlled isomerization of the initially formed branched products. The isomerization is promoted by protic acid and active palladium catalyst. The use of base shuts down the isomerization pathway and allows for the preparation and isolation of branched allylic amines. Solvent plays a key role in achieving high kinetic regioselectivity and in controlling the rate of isomerization. The isomerization can be combined with ring-closing metathesis to afford the synthesis of exocyclic allylic amines from their endocyclic precursors.