1-benzyl-4-methyl-4-vinylazetidine | 1198423-01-6

• 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: 1-benzyl-4-methyl-4-vinylazetidine
• 英文别名: 1-benzyl-2-methyl-2-vinylazetidine；N-benzyl-2-methyl-2-vinylazetidine；1-Benzyl-2-ethenyl-2-methylazetidine；1-benzyl-2-ethenyl-2-methylazetidine
• CAS: 1198423-01-6
• 化学式: C₁₃H₁₇N
• 分子量: 187.285
• InChiKey: VAVNRKWVJLHBJF-UHFFFAOYSA-N

物化性质

• 沸点：
  237.9±29.0 °C(Predicted)
• 密度：
  1.042±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-benzyl-4-methyl-4-vinylazetidine 在 吗啉 、 bis(η3-allyl-μ-chloropalladium(II)) 、 三氟乙酸 、 亚磷酸三乙酯 作用下， 以 二氯甲烷 为溶剂， 反应 10.0h， 以97%的产率得到1-苄基-4-甲基-1,2,3,6-四氢吡啶
  参考文献：
  名称：

  钯催化环烯丙基胺的缩环和扩环反应

  摘要：

  在玫瑰色上环绕：氨基可以充当钯催化的烯丙基胺化反应中的离去基团或亲核试剂。结果，容易获得的环胺可以收缩或扩环（参见方案）。

  DOI：

  10.1002/anie.201100612
• 作为产物：
  描述：

  4-methyl-4-vinylazetidin-2-one 在 aluminum (III) chloride 、 lithium aluminium tetrahydride 、 sodium hydride 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 生成 1-benzyl-4-methyl-4-vinylazetidine
  参考文献：
  名称：

  钯催化环烯丙基胺的缩环和扩环反应

  摘要：

  在玫瑰色上环绕：氨基可以充当钯催化的烯丙基胺化反应中的离去基团或亲核试剂。结果，容易获得的环胺可以收缩或扩环（参见方案）。

  DOI：

  10.1002/anie.201100612

文献信息

• Synthesis of Eight‐Membered Lactams through Formal [6+2] Cyclization of Siloxy Alkynes and Vinylazetidines
  作者：An Wu、Qiang Feng、Herman H. Y. Sung、Ian D. Williams、Jianwei Sun

  DOI：10.1002/anie.201902866

  日期：2019.5.13

  lactams through formal [6+2] cyclization of siloxy alkynes and vinylazetidines has been developed. Evidence from a chirality transfer experiment suggests that the reaction proceeds via a [3,3]‐sigmatropic rearrangement from a ketene intermediate. This insight led to the development of alternative conditions and use of acyl chlorides as ketene precursors for the [6+2] reaction with vinylazetidines.

  通过硅烷氧基炔烃和乙烯基氮杂环丁烷的正式[6 + 2]环化，已经开发出一种有效合成八元内酰胺的新方法。手性转移实验的证据表明，该反应是通过乙烯酮中间体的[3,3]-σ重排而进行的。这种见解导致了替代条件的发展，并使用了酰氯作为与乙烯基氮杂环丁烷的[6 + 2]反应的乙烯酮前体。
• 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.
• Selective Synthesis of Eight-Membered Cyclic Ureas by the [6 + 2] Cycloaddition Reaction of 2-Vinylazetidines and Electron-Deficient Isocyanates
  作者：Shunsuke Koya、Kenichi Yamanoi、Ryu Yamasaki、Isao Azumaya、Hyuma Masu、Shinichi Saito

  DOI：10.1021/ol902299p

  日期：2009.12.3

  The [6 + 2] cycloaddition reaction of 2-vinylazetidines with electron-deficient isocyanates such as tosyl Isocyanate proceeded smoothly in the absence of the catalyst at room temperature, and various cyclic ureas were isolated in good to high yields. Electron-deficient allenes also reacted with the 2-vinylazetidine, and the corresponding azocine derivatives were isolated.
• Palladium-Catalyzed Ring-Contraction and Ring-Expansion Reactions of Cyclic Allyl Amines
  作者：Igor Dubovyk、Dmitry Pichugin、Andrei K. Yudin

  DOI：10.1002/anie.201100612

  日期：2011.6.20

  Ring around the rosy: An amino group can act as the leaving group or the nucleophile in a palladium‐catalyzed allylic amination. As a result, readily accessible cyclic amines can be either ring contracted or ring expanded (see scheme).

  在玫瑰色上环绕：氨基可以充当钯催化的烯丙基胺化反应中的离去基团或亲核试剂。结果，容易获得的环胺可以收缩或扩环（参见方案）。