ethyl (E)-5-methyl-2,4-hexadienoate | 54542-32-4

• 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 (E)-5-methyl-2,4-hexadienoate
• 英文别名: ethyl (E)-5-methylhexa-2,4-dienoate；5-Methyl-sorbic Acid Ethyl Ester；ethyl (2E)-5-methylhexa-2,4-dienoate
• CAS: 54542-32-4
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: WANQTLPABDXASE-FNORWQNLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 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 (E)-5-methyl-2,4-hexadienoate 在 Lindlar's catalyst 氢气 作用下， 以 乙醇 为溶剂， 25.0 ℃ 、10.13 MPa 条件下， 生成 6-甲基-2-庚酮
  参考文献：
  名称：

  A total synthesis of phytol

  摘要：

  DOI：

  10.1021/jo01277a043
• 作为产物：
  描述：

  山梨酸乙酯 在 正丁基锂 、 臭氧 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 ethyl (E)-5-methyl-2,4-hexadienoate
  参考文献：
  名称：

  Long-acting contraceptive agents: Norethisterone esters of polyunsaturated acids

  摘要：

  Some new derivatives of norethisterone (17 alpha-ethynyl-17 beta-hydroxyestr-4-en-3-one) are described in which the 17 beta-hydroxyl group of the steroid is esterified with polyunsaturated aliphatic acids. The potential of these compounds as long-acting contraceptive agents has been evaluated.

  DOI：

  10.1016/0039-128x(83)90098-3

文献信息

• Cobalt-Catalyzed Diastereo- and Enantioselective Reductive Allyl Additions to Aldehydes with Allylic Alcohol Derivatives via Allyl Radical Intermediates
  作者：Lei Wang、Lifan Wang、Mingxia Li、Qinglei Chong、Fanke Meng

  DOI：10.1021/jacs.1c05690

  日期：2021.8.18

  enantioenriched homoallylic alcohols with a remarkably broad scope of allyl groups that can be introduced. Mechanistic studies indicated that allyl radical intermediates were involved in this process. These new discoveries establish a new strategy for development of enantioselective transformations through capture of radicals by chiral Co complexes, pushing forward the frontier of Co complexes for enantioselective

  催化生成两亲性 π-烯丙基-金属配合物及其在对映选择性转化中的应用构成了将烯丙基引入分子的有效方法。本文提出了一种前所未有的钴催化的高度位点、非对映和对映选择性方案，用于立体选择性形成亲核烯丙基-Co(II) 配合物，然后加入醛。该反应的特点是将容易获得的烯丙醇衍生物非对映和对映收敛转化为多样化的富含对映体的高烯丙醇，其中可以引入的烯丙基范围非常广泛。机理研究表明，烯丙基自由基中间体参与了这一过程。
• First synthesis, X-ray structure analysis and reactions of alkenyltriphenylbismuthonium salts
  作者：Yoshihiro Matano、Masanori Yoshimune、Nagao Azuma、Hitomi Suzuki

  DOI：10.1039/p19960001971

  日期：——

  Treatment of triphenylbismuth difluoride with alkenyltrimethylsilanes 1 or trimethylsilyl cyanide–alkenyltrialkylstannanes 3 in the presence of boron trifluoride–diethyl ether gave the corresponding alkenyltriphenylbismuthonium tetrafluoroborates 2 in moderate to good yields. An X-ray crystallographic analysis of the salt 2e confirmed the distorted tetrahedral geometry of the central bismuth atom. When treated with a sulfinate 5 or the thiolate 11, the salts 2 readily transferered both the vinyl and phenyl moieties to these nucleophiles to afford the sulfones 7–10 or the sulfides 12, 13, respectively. In the presence of a palladium catalyst, the salt 2e underwent the Heck-type reaction with ethyl acrylate 17 to afford the dienoate 18 and cinnamate 19 in moderate yields. Action of KOBut on the salt 2b yielded p-tolylacetylene 22, while a similar reaction with the salt 2e in the presence of the styrenes 23 gave the cyclopropanes 24. A Hammett study of the latter reaction has suggested a possible involvement of an alkylidenecarbene as the intermediate in these base-promoted reactions.

  三苯基二氟化铋与烯基三甲基硅烷1或三甲基硅氰基-烯基三烷基锡烷3在三氟化硼-乙醚存在下反应，以中等至良好收率得到相应的烯基三苯基铋鎓四氟硼酸盐2。盐2e的X射线晶体学分析证实了中心铋原子扭曲的四面体几何结构。当与亚砜5或硫醇盐11处理时，盐2容易将乙烯基和苯基部分转移到这些亲核试剂上，分别得到砜7-10或硫化物12、13。在钯催化剂的存在下，盐2e与丙烯酸乙酯17发生 Heck 型反应，以中等收率得到二烯酸酯18和肉桂酸酯19。KOBut 对盐2b的作用产生了对甲苯乙炔22，而在苯乙烯23的存在下，盐2e的类似反应得到了环丙烷24。后一反应的 Hammett 研究表明，这些碱促进的反应中可能涉及一个烯基碳烯中间体。
• Pushing the Boundaries of Vinylogous Reactivity: Catalytic Enantioselective Mukaiyama Aldol Reactions of Highly Unsaturated 2-Silyloxyindoles
  作者：Claudio Curti、Andrea Sartori、Lucia Battistini、Nicoletta Brindani、Gloria Rassu、Giorgio Pelosi、Alessio Lodola、Marco Mor、Giovanni Casiraghi、Franca Zanardi

  DOI：10.1002/chem.201500083

  日期：2015.4.20

  The first example of catalytic, enantioselective hypervinylogous Mukaiyama aldol reaction (HVMAR) involving multiply unsaturated 2‐silyloxyindoles is reported. The reaction utilizes a chiral Lewis base‐catalyzed Lewis acid‐mediated technology to deliver homoallylic 3‐polyenylidene 2‐oxindoles with extraordinary levels of regio‐, enantio‐, and geometrical selectivity. This work highlights a subtle yet

  报道了涉及多个不饱和2-甲硅烷基氧基吲哚的催化，对映选择性高乙烯基MukaiyaMA aldol反应（HVMAR）的第一个例子。该反应利用手性Lewis碱催化的Lewis酸介导的技术，可提供具有极高的区域，对映体和几何选择性的均聚物3-聚亚苯基2-吲哚。这项工作强调了吲哚N-取代基对施主底物的乙烯基反应空间传播的微妙而决定性的影响，距离乙烯基效应的起源最多十个键。分析13同源甲硅烷基氧基吲哚供体中C-ω远程位点的C NMR化学位移使结果合理化，并容易对给定醛受体的HVMAR反应性/惰性进行定性预测。
• Direct hydroperoxygenation of conjugated olefins catalyzed by cobalt(II) porphyrin
  作者：Kazuhiro Sugamoto、Yoh-ichi Matsushita、Takanao Matsui

  DOI：10.1039/a805888a

  日期：——

  A novel and direct synthesis of hydroperoxy compounds from various types of conjugated olefins was established via cobalt(II) porphyrin-catalyzed hydroperoxygenation. The reaction of α,β,γ,δ-unsaturated carbonyl compounds, acrylic esters, α-substituted acrylic esters and styrene derivatives with molecular oxygen and triethylsilane in the presence of a catalytic amount of cobalt(II) porphyrin proceeded

  通过钴（II）卟啉催化的加氢过氧反应，建立了由各种类型的共轭烯烃新型直接合成加氢过氧化合物的方法。在催化量的钴（II）卟啉存在下，α，β，γ，δ-不饱和羰基化合物，丙烯酸酯，α-取代的丙烯酸酯和苯乙烯衍生物与分子氧和三乙基硅烷的反应迅速进行，得到相应的加氢过氧化的化合物，产率高或中等。
• Silylene-Mediated Polarity Reversal of Dienoates: Additions of Dienoates to Aldehydes at the δ-Position To Form <i>trans</i>-Dioxasilacyclononenes
  作者：Christian C. Ventocilla、K. A. Woerpel

  DOI：10.1021/ja109631z

  日期：2011.1.26

  trans-dioxasilacyclononenes as single stereoisomers. This reaction, which converts the δ-position of the unsaturated carbonyl compound into a nucleophilic center, represents an inversion of polarity from the normal pattern of reactivity. The stereospecificity of the reaction suggests that the addition to aldehydes occurred through a closed, chairlike six-membered transition state. This reaction can be

  亚甲硅烷向 α,β,γ,δ-不饱和羰基化合物的转移产生了氧杂硅杂环戊烯，这些杂硅杂环戊烯经过与醛的热加成以产生作为单一立体异构体的反式二氧杂硅杂环壬烯。该反应将不饱和羰基化合物的 δ 位转化为亲核中心，代表了正常反应模式的极性反转。该反应的立体特异性表明醛的加成是通过一个封闭的、椅子状的六元过渡态发生的。通过使用手性助剂来控制氧硅杂环戊烯的形成，该反应可用于制备对映体纯材料。所得反式环烯烃的官能化完全立体选择性地发生。