5,5-dicyano-2,6,9-trimethyl-4-phenyldeca-1,7-diene

• 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: 5,5-dicyano-2,6,9-trimethyl-4-phenyldeca-1,7-diene
• 英文别名: 2-[(E)-5-methylhex-3-en-2-yl]-2-(3-methyl-1-phenylbut-3-enyl)propanedinitrile
• 化学式: C₂₁H₂₆N₂
• 分子量: 306.451
• InChiKey: UUNAZMCBGMITJR-VAWYXSNFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  47.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  苄烯丙二腈 、 (E)-2-chloro-5-methylhex-3-ene 、 甲基烯丙基三正丁基锡 在 四(三苯基膦)钯 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以69%的产率得到5,5-dicyano-2,6,9-trimethyl-4-phenyldeca-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

文献信息

• 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.