[(E)-1-chlorobut-2-enyl]cyclohexane | 335627-62-8

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氯化物
• 英文名称: [(E)-1-chlorobut-2-enyl]cyclohexane
• CAS: 335627-62-8
• 化学式: C₁₀H₁₇Cl
• 分子量: 172.698
• InChiKey: YLTQDTMCFMJUOR-QHHAFSJGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  苄烯丙二腈 、 烯丙基三丁基锡 、 [(E)-1-chlorobut-2-enyl]cyclohexane 在 四(三苯基膦)钯 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以78%的产率得到5,5-dicyano-8-cyclohexyl-6-methyl-4-phenylocta-1,7-diene
  参考文献：
  名称：

  Control of the Regioselectivity in Catalytic Transformations Involving Amphiphilic Bis-allylpalladium Intermediates:  Mechanism and Synthetic Applications

  摘要：

  Various dialkyl-substituted allyl chloride derivatives (2d-i) undergo regioselective palladium-catalyzed coupling reactions with allylstannanes (1a,b) and benzylidenemalonitrile (4), providing functionalized 1,7-octadienes in good yield. The catalytic reaction proceeds through an unsymmetrical amphiphilic bis-allylpalladium intermediate. An:introductory electrophilic attack on the terminal position of the unsubstituted alkyl moiety is followed by a nucleophilic attack on the alkyl-substituted allyl ligand. A theoretical analysis was performed by applying density functional theory at the B3PW91/DZ+P level to study the substituent effects on the electrophilic attack. According to the theoretical results, the high regioselectivity can be ascribed to the electronic effects of the alkyl substituents: The terminal alkyl groups destabilize the eta (1),eta (3)-bis-allylpalladium intermediate of the reaction; in addition, the alkyl substitution increases the activation barrier for the electrophilic attack.

  DOI：

  10.1021/jo001374d
• 作为产物：
  描述：

  1-环己基-2-丁烯醇 在 三聚氯氰 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 [(E)-3-chlorobut-1-enyl]cyclohexane 、 [(E)-1-chlorobut-2-enyl]cyclohexane
  参考文献：
  名称：

  氰尿酰氯介导的烯丙基氯化物合成——原位与远位取代

  摘要：

  摘要 使用氰尿酰氯与 DMF 结合通过同位取代和远位取代，通过明智地选择不对称烯丙醇适当位置上的取代基，注意其电子和空间性质，合成了不对称烯丙基氯。

  DOI：

  10.1080/00397910701578206

文献信息

• Palladium-Catalyzed Tandem Bis-allylation of Isocyanates
  作者：Niclas Solin、Sanjay Narayan、Kálmán J. Szabó

  DOI：10.1021/ol015545s

  日期：2001.3.1

  [GRPAHICS]A tandem bis-allylation of p-toluenesulfonyl isocyanate can be achieved by palladium-catalyzed three-component coupling reaction with allylstannanes and allyl chlorides, A high level of regioselectivity can be obtained by the appropriate choice of the allylic substituents. The reaction mechanism and the regiochemistry of the reaction can be explained by formation of an amphoteric bis-allylpalladium intermediate, This bis-allylpalladium intermediate undergoes an initial electrophilic attack on one of the allyl moieties followed by a nucleophilic attack on the other.
• Cyanuric Chloride–Mediated Synthesis of Allylic Chloride—<i>ipso</i>‐ versus<i>tele</i>‐Substitution
  作者：Sanchita Roy、Tarak Das、Manabendra Saha、Subrata Kumar Chaudhuri、Sanjay Bhar

  DOI：10.1080/00397910701578206

  日期：2007.11

  Abstract Synthesis of unsymmetrical allylic chlorides has been accomplished using cyanuric chloride in combination with DMF through ipso‐substitution and tele‐substitution by judicious choice of the substituents at appropriate positions of unsymmetrical allyl alcohols, taking care of their electronic and steric properties.

  摘要 使用氰尿酰氯与 DMF 结合通过同位取代和远位取代，通过明智地选择不对称烯丙醇适当位置上的取代基，注意其电子和空间性质，合成了不对称烯丙基氯。
• Control of the Regioselectivity in Catalytic Transformations Involving Amphiphilic Bis-allylpalladium Intermediates:  Mechanism and Synthetic Applications
  作者：Niclas Solin、Sanjay Narayan、Kálmán J. Szabó

  DOI：10.1021/jo001374d

  日期：2001.3.1

  Various dialkyl-substituted allyl chloride derivatives (2d-i) undergo regioselective palladium-catalyzed coupling reactions with allylstannanes (1a,b) and benzylidenemalonitrile (4), providing functionalized 1,7-octadienes in good yield. The catalytic reaction proceeds through an unsymmetrical amphiphilic bis-allylpalladium intermediate. An:introductory electrophilic attack on the terminal position of the unsubstituted alkyl moiety is followed by a nucleophilic attack on the alkyl-substituted allyl ligand. A theoretical analysis was performed by applying density functional theory at the B3PW91/DZ+P level to study the substituent effects on the electrophilic attack. According to the theoretical results, the high regioselectivity can be ascribed to the electronic effects of the alkyl substituents: The terminal alkyl groups destabilize the eta (1),eta (3)-bis-allylpalladium intermediate of the reaction; in addition, the alkyl substitution increases the activation barrier for the electrophilic attack.