[(1E)-4,5-dimethylhexa-1,4-dien-1-yl]benzene

• 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: [(1E)-4,5-dimethylhexa-1,4-dien-1-yl]benzene
• 英文别名: ((E)-4,5-dimethylhexa-1,4-dienyl)benzene；(4,5-dimethylhexa-1,4-dien-1-yl)benzene；(E)-4,5-dimethyl-1-phenyl-1,4-hexadiene；(E)-4,5-dimethyl-1-phenylhexa-1,4-diene；[(1E)-4,5-dimethylhexa-1,4-dienyl]benzene
• 化学式: C₁₄H₁₈
• 分子量: 186.297
• InChiKey: UXJYCXSSWBDWIA-YRNVUSSQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 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：

  [(1E)-4,5-dimethylhexa-1,4-dien-1-yl]benzene 在 (η6-naphthalene)(η4-1,5-cyclooctadiene)ruthenium(0) 作用下， 以 氘代苯 为溶剂， 反应 148.0h， 生成 (E)-4,5-dimethyl-1-phenylhexa-2,4-diene
  参考文献：
  名称：

  Mechanistic insights into catalytic linear cross-dimerization between conjugated dienes and styrenes by a ruthenium(0) complex

  摘要：

  The mechanistic studies for linear cross-dimerization between 2,3-dimethylbuta-1,3-diene and styrene by a Ru(0) complex, Ru(eta(6)-naphthalene)(eta(4)-1,5-COD) (1), are performed both by kinetic and computational studies. This reaction is basically zero-order to both of the diene and styrene concentrations and first-order to the catalyst concentration. The Hammett plot using p-substituted styrenes gives a linear relationship with a positive slope (rho = +0.482). The deuterium isotope experiment clearly shows the present reaction being a formal 1,4-addition of a C-H bond in styrene to cisoid-1,3-diene. These kinetic studies show the reaction proceeding via oxidative coupling mechanism that is also supported by the DFT calculations. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2015.08.022
• 作为产物：
  描述：

  (E)-4,5-dimethyl-1-phenylhexa-2,4-diene 在 (η6-naphthalene)(η4-1,5-cyclooctadiene)ruthenium(0) 作用下， 以 氘代苯 为溶剂， 反应 148.0h， 生成 [(1E)-4,5-dimethylhexa-1,4-dien-1-yl]benzene
  参考文献：
  名称：

  Mechanistic insights into catalytic linear cross-dimerization between conjugated dienes and styrenes by a ruthenium(0) complex

  摘要：

  The mechanistic studies for linear cross-dimerization between 2,3-dimethylbuta-1,3-diene and styrene by a Ru(0) complex, Ru(eta(6)-naphthalene)(eta(4)-1,5-COD) (1), are performed both by kinetic and computational studies. This reaction is basically zero-order to both of the diene and styrene concentrations and first-order to the catalyst concentration. The Hammett plot using p-substituted styrenes gives a linear relationship with a positive slope (rho = +0.482). The deuterium isotope experiment clearly shows the present reaction being a formal 1,4-addition of a C-H bond in styrene to cisoid-1,3-diene. These kinetic studies show the reaction proceeding via oxidative coupling mechanism that is also supported by the DFT calculations. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2015.08.022

文献信息

• Direct Cross-Coupling of Allylic C(sp³ )−H Bonds with Aryl- and Vinylbromides by Combined Nickel and Visible-Light Catalysis
  作者：Long Huang、Magnus Rueping

  DOI：10.1002/anie.201805118

  日期：2018.8.6

  An efficient protocol for the direct allylic C(sp3)−H bond activation of unactivated tri‐ and tetrasubstituted alkenes and their functionalization with aryl‐ and vinylbromides by nickel and visible‐light photocatalysis has been developed. The method allows C(sp2)−C(sp3) formation under mild reaction conditions with good functional‐group tolerance and excellent regioselectivity.

  已经开发了一种有效的协议，用于未活化的三取代和四取代的烯烃的直接烯丙基C（sp 3）-H键活化以及镍和可见光光催化作用将它们用芳基和乙烯基溴官能化。该方法可以在温和的反应条件下形成C（sp 2）-C（sp 3），具有良好的官能团耐受性和极好的区域选择性。
• In Situ Routes to Catalytically Active Ru(0) Species by Reduction of Readily Available, Air-Stable Precursors
  作者：Masafumi Hirano、Hideyuki Kobayashi、Takao Ueda、Yuki Hiroi、Ryota Abe、Nobuyuki Komine、Annie L. Colebatch、Martin A. Bennett

  DOI：10.1021/acs.organomet.7b00882

  日期：2018.4.9

  Ru(0) compound. Interestingly, this in situ reduction method of Ru(II) using BuLi can be applied to the cross-dimerization using an ester such as methyl acrylate. Alternatively, an air-stable Ru(II) complex having a labile arene ligand such as [RuCl2(η6-anisole)]2 (5c) (5 mol %) with Na2CO3 (40 mol %) in the presence of 1,5-COD (20 mol %) at 100 °C for 6 h in 2-butanol also catalyzes the same cross-dimerization

  已经实现了通过原位还原空气稳定的Ru（II）催化剂前体催化的共轭二烯与取代烯烃的交叉二聚。2,3-二甲基苯乙烯的反应通过的[Ru（ACAC）催化2（η 4 -1,5-二COD）]（2A用BuLi（10摩尔％），在50）（5摩尔％）℃6在己烷中反应24小时，以99％的产率得到交叉二聚体（（E）-4,5-二甲基-1-苯基六-1,4-二烯（3a）/（E）-4,5-二甲基-1-苯基六烯-2,4-二烯（3b）/异构体= 84/9/7）。因为2a和BuLi都不单独催化交叉二聚和在萘存在下用BuLi还原2a会产生[Ru（η6 -萘）（η 4 -1,5-二COD）]（1A），在该催化活性物质被认为是由Ru（0）化合物。有趣的是，这种使用BuLi的Ru（II）原位还原方法可以应用于使用诸如丙烯酸甲酯的酯的交叉二聚反应。可替代地，空气稳定的钌（II）具有不稳定芳烃配体如复杂的合成将[RuCl 2（η 6 -苯甲醚）]
• Nickel-catalysed addition of organoboronates to 1,3-dienesElectronic supplementary information (ESI) available: 1H NMR spectra and MS data. See http://www.rsc.org/suppdata/cc/b2/b207185a/
  作者：Eiji Shirakawa、Go Takahashi、Teruhisa Tsuchimoto、Yusuke Kawakami

  DOI：10.1039/b207185a

  日期：2002.9.23

  Aryl- and alkenylboronates were found to add to 1,3-dienes in the presence of a catalytic amount of bis(1,5-cyclooctadiene)nickel, where a proton source in combination with a solvent considerably controls the regioselectivity.

  在双(1,5-环辛二烯)镍的催化下，发现芳基和烯基硼酸盐可与 1,3-二烯相加，其中质子源与溶剂的结合在很大程度上控制了区域选择性。
• Iron-Catalyzed 1,4-Addition of α-Olefins to Dienes
  作者：Benoît Moreau、Jessica Y. Wu、Tobias Ritter

  DOI：10.1021/ol802524r

  日期：2009.1.15

  A new intermolecular, stereo- and regioselective iron-catalyzed 1,4-addition of α-olefins to 1,3-dienes using as low as 1 mol % of an iminopyridine−ferrous chloride complex was developed. Importantly, both double bonds of the linear 1,4-diene addition products are obtained with absolute stereocontrol.

  使用低至1 mol％的亚氨基吡啶-氯化亚铁络合物，开发了一种新的分子间，立体和区域选择性铁催化的α-烯烃向1,3-二烯的1,4-加成反应。重要的是，在绝对立体控制下获得线性1，4-二烯加成产物的两个双键。
• Gaining Absolute Control of the Regiochemistry in the Cobalt-Catalyzed 1,4-Hydrovinylation Reaction
  作者：Marion Arndt、Mehmet Dindaroğlu、Hans-Günther Schmalz、Gerhard Hilt

  DOI：10.1021/ol202696n

  日期：2011.12.2

  The absolute control of the regiochemistry of a cobalt-catalyzed 1,4-hydrovinylation reaction is achieved by alternation of the ligands applied. While the dppe/dppp ligands led to the formation of the branched product, the herein described application of the SchmalzPhos ligand generates the corresponding linear product in both excellent yields and regioselectivities. The catalyst system exhibits a high tolerance toward functional groups, and the very mild reaction conditions allow the synthesis of 1,4-dienes without isomerization into conjugated systems.