(E)-ethyl 2,2-dimethyl-5-phenylpent-4-enoate | 72524-20-0

• 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)-ethyl 2,2-dimethyl-5-phenylpent-4-enoate
• 英文别名: ethyl (E)-2,2-dimethyl-5-phenylpent-4-enoate；ethyl 2,2-dimethyl-5-phenyl-4-pentenoate
• CAS: 72524-20-0
• 化学式: C₁₅H₂₀O₂
• 分子量: 232.323
• InChiKey: MBBGUJKRDITEET-DHZHZOJOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  (E)-ethyl 2,2-dimethyl-5-phenylpent-4-enoate 在 吡啶 、 lithium aluminium tetrahydride 、 Jones reagent 、 盐酸羟胺 、 碘 、 silica gel 、 magnesium 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 (1E,5E)-4,4-dimethyl-1-phenyldeca-1,9-dien-5-one oxime
  参考文献：
  名称：

  Iminoxyl Radical-Promoted Dichotomous Cyclizations: Efficient Oxyoximation and Aminooximation of Alkenes

  摘要：

  A novel iminoxyl radical-involved metal-free approach to vicinal oxyoximation and aminooximation of unactivated alkenes is developed. This method utilizes the dichotomous reactivity of the iminoxyl radical to furnish a general difunctionalization on alkenes using simple tert-butyl nitrite (TBN) as the iminoxyl radical initiator as well the carbon radical trap. By using this protocol, oxime featured 4,5-dihydroisoxazoles and cyclic nitrones were facilely prepared from beta,gamma- and gamma,delta-unsaturated ketoximes, respectively.

  DOI：

  10.1021/ol502258n
• 作为产物：
  描述：

  N-(quinolin-8-yl)pivalamide 在 三氟化硼乙醚 、 sodium acetate 、 nickel diacetate 、 溶剂黄146 、 二苯基甲氧基膦 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 60.0h， 生成 (E)-ethyl 2,2-dimethyl-5-phenylpent-4-enoate
  参考文献：
  名称：

  Nickel-Catalyzed Stereoselective Alkenylation of C(sp³)–H Bonds with Terminal Alkynes

  摘要：

  A nickel-catalyzed stereoselective alkenylation of an unactivated beta-C(sp(3))-H bond in aliphatic amide with terminal alkynes using 8-aminoquinoline auxiliary is reported for the first time. This reaction displays excellent functional group tolerance with respect to both aliphatic amides and terminal alkynes and features a cheap nickel catalytic system. The 8-aminoquinolyl directing group could be smoothly removed, and the resultant beta-styrylcarboxylic acid derivatives could serve as versatile building blocks for further transformation.

  DOI：

  10.1021/acs.orglett.6b03856

文献信息

• Intramolecular hydroalkoxylation in Brønsted acidic ionic liquids and its application to the synthesis of (±)-centrolobine
  作者：Yunkyung Jeong、Do-Young Kim、Yunsil Choi、Jae-Sang Ryu

  DOI：10.1039/c0ob00701c

  日期：——

  The SO3H-tethered imidazolium and triazolium salts, nonvolatile and recyclable Brønsted acidic ionic liquids, efficiently mediate intramolecular hydroalkoxylations of alkenyl alcohols. They have been successfully employed in the synthesis of (±)-centrolobine.

  SO 3 H系咪唑鎓盐和三唑鎓盐，不挥发且可回收的布朗斯台德酸性离子液体，可有效介导链烯醇的分子内加氢烷氧基化反应。它们已成功地用于合成（±）-中心洛宾。
• Asymmetric cyclopropanation of ketene silyl acetal with allylic acetate catalyzed by a palladium complex
  作者：Akiharu Satake、Hitomi Kadohama、Hiroyuki Koshino、Tadashi Nakata

  DOI：10.1016/s0040-4039(99)00582-1

  日期：1999.4

  The first asymmetric cyclopropanation of ketene silyl acetal with allylic acetate was achieved. New chiral oxazolidinylpyrazole ligands and their η3-allylpalladium complexes were synthesized. Reaction of cinnamyl acetate with ketene silyl acetal of ethyl isobutylate in the presence of a palladium complex gave a phenyl cyclopropane derivative in 20∼ 54%ee.

  乙烯酮乙酸乙烯酯实现了乙烯酮甲硅烷基乙缩醛的首次不对称环丙烷化。新的手性配体oxazolidinylpyrazole及其η 3 π-烯丙基配合物的合成。在钯配合物的存在下，使肉桂酸乙酸肉桂酯与异丁酸乙酯的乙烯酮甲硅烷基缩醛反应，得到20〜54％ee的苯基环丙烷衍生物。
• Novel η³-Allylpalladium−Pyridinylpyrazole Complex:  Synthesis, Reactivity, and Catalytic Activity for Cyclopropanation of Ketene Silyl Acetal with Allylic Acetates
  作者：Akiharu Satake、Tadashi Nakata

  DOI：10.1021/ja982269c

  日期：1998.10.1

  Novel cationic η3-allylpalladium−pyridinylpyrazole complexes 1a and 1b were synthesized from 3-alkyl-5-(2-pyridinyl)pyrazole and η3-allylpalladium chloride dimer in the presence of AgBF4. Cationic complexes 1a and 1b were converted into neutral complexes 2a and 2b under basic conditions. These complexes were characterized by 1H, 13C, and 15N NMR studies. Neutral complexes 2a and 2b have high catalytic

  在AgBF4 存在下，由3-烷基-5-(2-吡啶基)吡唑和η3-烯丙基氯化钯二聚体合成了新型阳离子η3-烯丙基钯-吡啶基吡唑配合物1a和1b。阳离子配合物1a和1b在碱性条件下转化为中性配合物2a和2b。这些配合物通过 1H、13C 和 15N NMR 研究表征。中性配合物 2a 和 2b 对烯酮甲硅烷基缩醛与烯丙乙酸酯的环丙烷化具有高催化活性。讨论了阳离子和中性配合物的比较和环丙烷化的反应机理。
• Cyclopropanation of Ketene Silyl Acetals with Allylic Acetates Using η³-Allylpalladium-Pyridinylimidazole Catalysts
  作者：Akiharu Satake、Hiroyuki Koshino、Tadashi Nakata

  DOI：10.1246/cl.1999.49

  日期：1999.1

  Highly selective cyclopropanation of ketene silyl acetals with allylic acetates was carried out in the presence of novel η3-allylpalladium-pyridinylimidazole complexes and sodium acetate in DMSO at room temperature. When cinnamyl acetate was used as an allylic acetate, phenylcyclopropane derivative was obtained stereoselectively in 83% yield.

  在新型 η3-烯丙基钯-吡啶基咪唑配合物和乙酸钠的存在下，在室温下，在 DMSO 中进行烯酮甲硅烷基缩醛与烯丙乙酸酯的高选择性环丙烷化反应。当乙酸肉桂酯用作乙酸烯丙酯时，苯基环丙烷衍生物以83%的收率立体选择性地获得。
• Facile synthesis of δ-ketoesters via formal two-carbon insertion into β-ketoesters
  作者：Yan Jiang、Song Xi、Qi Wang、Lin Fu、Ling He、Zhen Wang、Min Zhang

  DOI：10.1016/j.tetlet.2022.153656

  日期：2022.3

  A formal two-carbon insertion into β-ketoesters with vinylmetal has been developed for the rapid synthesis of δ-ketoesters. This method features high efficiency, simple operation, and mild conditions without the usage of bases and catalysts. The reaction is postulated to proceed via a tandem process involving nucleophilic addition of vinylmetal to ketone, retro-aldol reaction to give an enolate anion

  已经开发了一种正式的用乙烯基金属将双碳插入到β-酮酯中的方法，用于快速合成δ-酮酯。该方法具有效率高、操作简单、条件温和等特点，无需使用碱和催化剂。假设该反应通过串联过程进行，包括乙烯基金属与酮的亲核加成、逆醛醇反应产生烯醇化物阴离子和烯酮，最后是这两种中间体的迈克尔加成。