ethyl 4-methylhex-4-enoate | 120059-99-6

• 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 4-methylhex-4-enoate
• CAS: 120059-99-6
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: YSFFFGCNKMPMQQ-UHFFFAOYSA-N

物化性质

• 沸点：
  90 °C(Press: 0.5 Torr)
• 密度：
  0.897±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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 4-methylhex-4-enoate 在 potassium peroxymonosulfate 、 cerium(III) chloride 、 Shi's ketone 、 二甲醇缩甲醛 、 potassium carbonate 作用下， 以 四氢呋喃 、 乙醚 、 乙腈 为溶剂， 反应 6.0h， 生成
  参考文献：
  名称：

  Sequential Enzymatic Epoxidation Involved in Polyether Lasalocid Biosynthesis

  摘要：

  Enantioselective epoxidation followed by regioselective epoxide opening reaction are the key processes in construction of the polyether skeleton. Recent genetic analysis of ionophore polyether biosynthetic gene dusters suggested that flavin-containing monooxygenases (FMOs) could be involved in the oxidation steps. In vivo and in vitro analyses of Lsd18, an FMO involved in the biosynthesis of polyether lasalocid, using simple olefin or truncated diene of a putative substrate as substrate mimics demonstrated that enantioselective epoxidation affords natural type mono- or bis-epoxide in a stepwise manner. These findings allow us to figure out enzymatic polyether construction in lasalocid biosynthesis.

  DOI：

  10.1021/ja301386g
• 作为产物：
  描述：

  乙基三苯基溴化膦 、 乙酰丙酸乙酯 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 15.0h， 以74%的产率得到ethyl 4-methylhex-4-enoate
  参考文献：
  名称：

  顺序式酰基硫醇-烯和硫磺内酯化法合成δ-硫代内酯

  摘要：

  已开发出一种从廉价且容易获得的γ-不饱和酯合成δ-硫代内酯的新策略。该策略将自由基酰基硫醇-烯反应纳入了关键的CS键形成步骤。通过5-巯基戊酸的Steglicch型硫内酯化来实现环化。我们报道了在温和的反应条件下，对中等官能团具有良好的收率的δ-硫代内酯的简便，可扩展合成，对一系列官能团具有耐受性。

  DOI：

  10.1021/acs.orglett.9b01271

文献信息

• Oxidative Catalysis Using the Stoichiometric Oxidant as a Reagent: An Efficient Strategy for Single-Electron-Transfer-Induced Tandem Anion-Radical Reactions
  作者：František Kafka、Martin Holan、Denisa Hidasová、Radek Pohl、Ivana Císařová、Blanka Klepetářová、Ullrich Jahn

  DOI：10.1002/anie.201403776

  日期：2014.9.8

  Oxidative single‐electron transfer‐catalyzed tandem reactions consisting of a conjugate addition and a radical cyclization are reported, which incorporate the mandatory terminal oxidant as a functionality into the product.

  据报道，由共轭加成和自由基环化反应组成的氧化单电子转移催化串联反应，将强制性末端氧化剂作为功能性产物结合到产品中。
• Iron-Mediated Photochemical Anti-Markovnikov Hydroazidation of Unactivated Olefins
  作者：Henry Lindner、Willi M. Amberg、Erick M. Carreira

  DOI：10.1021/jacs.3c09122

  日期：2023.10.18

  Unactivated olefins are converted to alkyl azides with bench-stable NaN3 in the presence of FeCl3·6H2O under blue-light irradiation. The products are obtained with anti-Markovnikov selectivity, and the reaction can be performed under mild ambient conditions in the presence of air and moisture. The transformation displays broad functional group tolerance, which renders it suitable for functionalization

  在蓝光照射下，在 FeCl 3 ·6H 2 O 存在下，未活化的烯烃与实验室稳定的 NaN 3转化为烷基叠氮化物。所得产物具有抗马可夫尼科夫选择性，反应可以在空气和湿气存在的温和环境条件下进行。该转化表现出广泛的官能团耐受性，这使其适合复杂分子的官能化。进行机理研究以深入了解叠氮反应并揭示水合铁中的水作为氢原子源的作用。
• A Sequential Acyl Thiol–Ene and Thiolactonization Approach for the Synthesis of δ-Thiolactones
  作者：Ruairí O. McCourt、Eoin M. Scanlan

  DOI：10.1021/acs.orglett.9b01271

  日期：2019.5.3

  A novel strategy for the synthesis of δ-thiolactones from inexpensive and readily available γ-unsaturated esters has been developed. This strategy incorporates a radical acyl thiol–ene reaction as the key C–S bond forming step. Cyclization is achieved via a Steglich-type thiolactonization of 5-mercaptopentanoic acids. We report the facile and scalable synthesis of δ-thiolactones in moderate to good

  已开发出一种从廉价且容易获得的γ-不饱和酯合成δ-硫代内酯的新策略。该策略将自由基酰基硫醇-烯反应纳入了关键的CS键形成步骤。通过5-巯基戊酸的Steglicch型硫内酯化来实现环化。我们报道了在温和的反应条件下，对中等官能团具有良好的收率的δ-硫代内酯的简便，可扩展合成，对一系列官能团具有耐受性。
• Sequential Enzymatic Epoxidation Involved in Polyether Lasalocid Biosynthesis
  作者：Atsushi Minami、Mayu Shimaya、Gaku Suzuki、Akira Migita、Sandip S. Shinde、Kyohei Sato、Kenji Watanabe、Tomohiro Tamura、Hiroki Oguri、Hideaki Oikawa

  DOI：10.1021/ja301386g

  日期：2012.5.2

  Enantioselective epoxidation followed by regioselective epoxide opening reaction are the key processes in construction of the polyether skeleton. Recent genetic analysis of ionophore polyether biosynthetic gene dusters suggested that flavin-containing monooxygenases (FMOs) could be involved in the oxidation steps. In vivo and in vitro analyses of Lsd18, an FMO involved in the biosynthesis of polyether lasalocid, using simple olefin or truncated diene of a putative substrate as substrate mimics demonstrated that enantioselective epoxidation affords natural type mono- or bis-epoxide in a stepwise manner. These findings allow us to figure out enzymatic polyether construction in lasalocid biosynthesis.