ethyl (2E,4E)-2-methylhexa-2,4-dienoate | 112182-01-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl (2E,4E)-2-methylhexa-2,4-dienoate
• 英文别名: ethyl (2E,4E)-2-methyl-2,4-hexadienoate；Ethyl 2-methylsorbate
• CAS: 112182-01-1
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: BTKGHSYBWGVHOE-GFGVWQOPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ethyl (2E,4E)-2-methylhexa-2,4-dienoate 在 sodium hydroxide 作用下， 以 叔丁醇 为溶剂， 反应 1.0h， 以69%的产率得到(2E,4E)-2-methyl-hexa-2,4-dienoic acid
  参考文献：
  名称：

  Antimicrobial metabolites produced by an intertidal Acremonium furcatum

  摘要：

  In a screening for antimicrobial metabolites, amides Of D-allo-and L-isoleucine derivatives were isolated from the culture of a marine strain of Acremonium furcatum. Structural elucidation of these compounds was performed by analysis of spectroscopic data and confirmed by synthesis. All of the compounds, natural and synthetic intermediates, were bioassayed against bacteria and phytopathogenic fungi, with many showing remarkable antifungal activities. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.phytochem.2006.07.028
• 作为产物：
  描述：

  ethyl E-2-methyl-3-hydroxyhex-4-enoate 在 phosphorus pentoxide 、 silica gel 作用下， 生成 ethyl (2E,4E)-2-methylhexa-2,4-dienoate
  参考文献：
  名称：

  Antimicrobial metabolites produced by an intertidal Acremonium furcatum

  摘要：

  In a screening for antimicrobial metabolites, amides Of D-allo-and L-isoleucine derivatives were isolated from the culture of a marine strain of Acremonium furcatum. Structural elucidation of these compounds was performed by analysis of spectroscopic data and confirmed by synthesis. All of the compounds, natural and synthetic intermediates, were bioassayed against bacteria and phytopathogenic fungi, with many showing remarkable antifungal activities. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.phytochem.2006.07.028

文献信息

• Ene–Diene Transmissive Cycloaddition Reactions with Singlet Oxygen: The <i>Vinylogous Gem Effect</i> and Its Use for Polyoxyfunctionalization of Dienes
  作者：Angelika Eske、Bernd Goldfuss、Axel G. Griesbeck、Alan de Kiff、Margarethe Kleczka、Matthias Leven、Jörg-M. Neudörfl、Moritz Vollmer

  DOI：10.1021/jo5000434

  日期：2014.2.21

  trimethylated substrates 1k and 1l, respectively. The vinylogous gem effect favors the formation of 1,3-dienes from the substrates, and thus, secondary singlet oxygen addition was observed to give hydroperoxy-1,2-dioxenes 19 and 20 in an ene–diene transmissive cycloaddition sequence. These products were reduced to give alcohols (16, 17, and 18) or furans (24 and 25), respectively, or treated with titanium(IV) alkoxides

  将模型化合物1b – d的单重态氧反应性和区域选择性与双（选择性）钛酸乙酯（1a）的单线态氧反应性和区域选择性进行了比较。tiglate / angelate系统1a / 1a'的动力学顺式效应为k E / k Z = 5.2，而高宝石区域选择性没有变化。与乙烯基的进一步缀合使得能够进行模式选择过程，即，[4 + 2]环加成对烯反应。对于二烯1e – g，研究了甲基化对烯键反应的模式选择性和区域选择性的位点特异性影响。。分别对γ，δ-二甲基化和α，γ，δ-三甲基化的底物1h和1i观察到乙烯基类宝石效应。相应的苯基化底物1j - 1显示出相似的模式选择性，因为单甲基化1j仅表现出[4 + 2]反应性，而串联产物12和14分别从二甲基化和三甲基化底物1k和1l中分离出来。乙烯基类宝石效应有利于从底物形成1,3-二烯，因此，观察到二次单线态氧的添加产生了氢过氧-1,2-二氧六环19和20以烯-二
• Efficient Silver-Catalyzed Regio- and Stereospecific Aziridination of Dienes
  作者：Josep Llaveria、Álvaro Beltrán、M. Mar Díaz-Requejo、M. Isabel Matheu、Sergio Castillón、Pedro J. Pérez

  DOI：10.1002/anie.201003167

  日期：2010.9.17

  Nitrene transfer: Unsymmetric dienes bearing a terminal hydroxy group can be regio‐ and stereospecifically converted into vinylaziridines upon nitrene transfer from PhINTs using a silver‐based catalyst. Stoichiometric mixtures of dienes and PhINTs were employed at low catalyst loadings (0.5 %; see scheme). The method has been applied to the synthesis of (±)‐sphingosine and gave good yields in a three‐step

  丁二烯转移：使用银基催化剂从PhINTs进行丁烯转移后，带有末端羟基的不对称二烯可以区域和立体定向转化为乙烯基氮丙啶。二烯烃和PhINTs的化学计量混合物以低催化剂负载量使用（0.5％；参见方案）。该方法已应用于（±）-鞘氨醇的合成，并通过三步操作获得了良好的收率。Ts = 4-甲苯磺酰基
• Rhodium-Catalyzed Synthesis of Eight-Membered Rings
  作者：Brenton DeBoef、W. Richard Counts、Scott R. Gilbertson

  DOI：10.1021/jo0620462

  日期：2007.2.1

  Experiments to develop a rhodium catalyst for the [4 + 2 + 2] cycloisomerization of dienynes with a second alkyne are described. The generality of the reaction is probed in terms of dienyne structure and alkyne structure. A catalyst system that provides cyclooctatrienes in greater than 70% yield is reported. Several experiments to determine the nature of the catalyst are described.

  描述了开发铑催化剂的实验，该铑催化剂用于用第二种炔烃进行二烯的[4 + 2 + 2]环异构化。根据二烯炔结构和炔烃结构探讨了反应的一般性。据报道，该催化剂体系提供的环辛烯的收率超过70％。描述了确定催化剂性质的几个实验。
• Total Synthesis of Leiodermatolide A via Transfer Hydrogenative Allylation, Crotylation, and Propargylation: Polyketide Construction beyond Discrete Allyl- or Allenylmetal Reagents
  作者：Yuk-Ming Siu、James Roane、Michael J. Krische

  DOI：10.1021/jacs.1c06062

  日期：2021.7.21

  The total synthesis of leiodermatolide A was accomplished in 13 steps (LLS). Transfer hydrogenative variants of three carbonyl additions that traditionally rely on premetalated reagents (allylation, crotylation, and propargylation) are deployed together in one total synthesis.

  leiodermatolide A 的全合成分 13 个步骤 (LLS) 完成。传统上依赖于预金属化试剂（烯丙基化、巴豆酰化和炔丙基化）的三种羰基加成的转移氢化变体在一个全合成中一起部署。
• Oxazaborolidinone-Mediated Asymmetric Bisvinylogous Mukaiyama Aldol Reaction
  作者：Alina Eggert、Christoph Etling、Lucas Millbrodt、Göran Schulz、Markus Kalesse

  DOI：10.1021/acs.orglett.1c03165

  日期：2021.11.19

  A bisvinylogous Mukaiyama aldol reaction using oxazaborolidinones as a source of chirality was developed. This methodology allows the fast assembly of conjugated dienols by expanding the vinylogy principle by two additional carbons, and can be conducted using a readily available Lewis acid at reasonable reaction times. A broad range of aromatic and aliphatic aldehydes can be used providing access to

  使用 oxazaborolidinones 作为手性来源的双乙烯基 Mukaiyama 醛醇反应被开发出来。该方法通过将乙烯学原理扩展为两个额外的碳，可以快速组装共轭二烯醇，并且可以使用现成的路易斯酸在合理的反应时间内进行。可以使用范围广泛的芳香族和脂肪族醛，为聚酮化合物的合成提供复杂的结构单元。