(E)-4-(3,3-dimethylbut-1-en-1-yl)benzonitrile | 41231-25-8

• 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: (E)-4-(3,3-dimethylbut-1-en-1-yl)benzonitrile
• 英文别名: 4-[(E)-3,3-dimethylbut-1-enyl]benzonitrile
• CAS: 41231-25-8
• 化学式: C₁₃H₁₅N
• 分子量: 185.269
• InChiKey: HVEDUKHIKIHNLF-CMDGGOBGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  4-((2R,3S)-3-tert-Butyl-4-oxo-oxetan-2-yl)-benzonitrile 以 various solvent(s) 为溶剂， 以100%的产率得到(E)-4-(3,3-dimethylbut-1-en-1-yl)benzonitrile
  参考文献：
  名称：

  2-氧杂环丁烷的热脱羧的哈米特相关性，溶剂效应和立体化学-两性离子中间体的证据

  摘要：

  2-氧杂环丁烷酮（和）热脱羧的动力学和立体化学数据表明，该反应通过两性离子中间体Z进行。

  DOI：

  10.1016/s0040-4039(00)71463-8

文献信息

• Copper- and Nickel-Catalyzed Cross-Coupling Reaction of Monofluoroalkenes with Tertiary, Secondary, and Primary Alkyl and Aryl Grignard Reagents
  作者：Hongyan Shi、Wenpeng Dai、Biyun Wang、Song Cao

  DOI：10.1021/acs.organomet.7b00859

  日期：2018.2.12

  with tertiary, secondary, and primary alkyl and aryl Grignard reagents in the presence of a catalytic amount of copper or nickel catalyst, respectively, has been developed. The reactions proceeded smoothly at room temperature, providing (E)-alkene isomers in moderate to high yields. Plausible mechanisms of the Ni-catalyzed coupling reaction of monofluoroalkene with Grignard reagents are suggested.

  已经开发了在催化量的铜或镍催化剂存在下，单氟烯烃分别与叔，仲，伯烷基和芳基格氏试剂的高效交叉偶联反应。反应在室温下顺利进行，以中等至高产率提供（E）-烯烃异构体。提出了单氟烯烃与格氏试剂在Ni催化下偶联反应的合理机理。
• Cu-mediated or metal-free alkylation of gem-dibromoalkenes with tertiary, secondary and primary alkyl Grignard reagents
  作者：Yupian Deng、Xuxue Zhang、Chuan Liu、Song Cao

  DOI：10.1016/j.tet.2020.131804

  日期：2021.2

  A novel copper-mediated or transition-metal-free alkylation of gem-dibromoalkenes with tertiary, secondary and primary alkyl Grignard reagents was described. The outcomes of these reactions were found to be highly dependent on the reaction conditions and the type of Grignard reagents used. Specifically, the tertiary alkylation of gem-dibromoalkenes proceeded efficiently in the presence of 50 mol% CuCN

  描述了用叔，仲和伯烷基格氏试剂对宝石-二溴烯烃进行新型的铜介导或无过渡金属的烷基化。发现这些反应的结果高度依赖于反应条件和所用格氏试剂的类型。具体地说，在50mol％的CuCN存在下或在无过渡金属的条件下，宝石-二溴烯烃的叔烷基化有效地进行，从而以高收率提供了叔烷基取代的单溴烯烃或烯烃。
• Metal-Free Oxidative Decarbonylative Hydroalkylation of Alkynes with Secondary and Tertiary Alkyl Aldehydes
  作者：Xuan-Hui Ouyang、Ren-Jie Song、Bang Liu、Jin-Heng Li

  DOI：10.1002/adsc.201501113

  日期：2016.6.16

  A new, metal‐free, radical‐mediated oxidative decarbonylative hydroalkylation of various alkynes with secondary and tertiary alkyl aldehydes using di‐tert‐butyl peroxide (DTBP) as oxidant is presented. This method enables the simultaneous formation of a CC bond and a CH bond through a sequence of decarbonylation, radical addition and protonation, and provides a straightforward route for transforming

  提出了一种新的，无金属，自由基介导的，使用过氧化二叔丁基（DTBP）作为氧化剂的仲炔和叔烷基醛与各种炔烃的氧化脱羰加氢烷基化反应。该方法能够同时形成一个C  C键和C 通过脱羰基加和质子化的序列H键，并且提供用于将炔烃到烯烃与二者的炔烃和烷基醛的高相容性的直接路由。
• Studies on the 1,2-Migrations in Pd-Catalyzed Negishi Couplings with JosiPhos Ligands
  作者：Anders T. Lindhardt、Thomas M. Gøgsig、Troels Skrydstrup

  DOI：10.1021/jo801824e

  日期：2009.1.2

  cross-coupling, which is promoted by palladium catalyst systems generated with JosiPhos ligands. Several of the factors that were demonstrated to be important for the 1,2-migration include (1) the nucleophilicity of the organometallic reagent, which possibly influences the transmetalation step in direct competition with the intermediate β-hydride elimination of the alkenyl Pd(II) species; (2) the structural

  我们报告了一项初步调查，目的是确定控制Negishi交叉偶联中1，2-迁移的因素，这是由JosiPhos配体生成的钯催化剂体系促进的。已证明对1,2-迁移很重要的几个因素包括（1）有机金属试剂的亲核性，这可能会影响烯基金属钯（II）的中间β-氢化物消除与直接竞争中的重金属化步骤） 物种; （2）甲苯磺酸甲苯酯和磷酸酯的结构特征，其中具有大体积C1取代基的底物在偶联反应条件下表现出最高的1，2-迁移倾向。（3）JosiPhos配体的结构，
• Unsymmetrical <i>E</i>-Alkenes from the Stereoselective Reductive Coupling of Two Aldehydes
  作者：Keyhan Esfandiarfard、Juri Mai、Sascha Ott

  DOI：10.1021/jacs.7b00428

  日期：2017.3.1

  The unprecedented formation of unsymmetrical alkenes from the intermolecular reductive coupling of two different aldehydes is described. In contrast to the McMurry reaction which affords statistical product mixtures, selectivity in the reported procedure is achieved by a sequential ionic mechanism in which a first aldehyde is reacted with a phosphanylphosphonate to afford a phosphaalkene intermediate

  描述了由两种不同醛的分子间还原偶联形成的前所未有的不对称烯烃。与提供统计产物混合物的 McMurry 反应相反，报告程序中的选择性是通过顺序离子机制实现的，其中第一个醛与膦酰基膦酸酯反应以提供磷烯烃中间体，该中间体在被氢氧化物活化后与第二个反应醛到不对称的 E-烯烃。所述反应不含过渡金属并且在环境温度下在几分钟内以良好至极好的总产率进行。这是一种使用原料醛直接生产含 C=C 双键产品的新方法，可能会影响未来化学家对多步合成序列的看法。