ethyl 3-oxooct-7-ynoate | 1000014-37-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: ethyl 3-oxooct-7-ynoate
• 英文别名: Ethyl 3-oxooct-7-ynoate
• CAS: 1000014-37-8
• 化学式: C₁₀H₁₄O₃
• 分子量: 182.219
• InChiKey: QVSAGTTVVJIAQC-UHFFFAOYSA-N

物化性质

• 沸点：
  254.9±20.0 °C(Predicted)
• 密度：
  1.023±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  13
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 3-oxooct-7-ynoate 在 zinc(II) chloride 、 ytterbium(III) triflate 作用下， 反应 24.0h， 以75%的产率得到2-甲基-6-氧代环己烯-1-羧酸乙酯
  参考文献：
  名称：

  Yb（OTf）3-促进的ZnCl2-催化的线性β-炔烃β-二羰基的Conia-Ene反应

  摘要：

  已经开发了一种原子经济且无溶剂的三氟甲磺酸（III）促进的氯化锌（II）催化的Conia-ene方法，用于构建五元至六元环的碳环。在氯化锌（II）和三氟甲磺酸（III）的存在下，在纯净条件下，以中等至良好的收率将各种线性的β-链烯基β-酮酸酯和β-链烯基β-二酮环化。值得注意的是，对五或六元环碳环的选择性取决于末端炔烃上的取代基。 氯化锌（II）-三氟甲磺酸（III）-Conia-ene反应-线性β-炔烃β-二羰基-碳环

  DOI：

  10.1055/s-0030-1258213
• 作为产物：
  描述：

  4-溴-1-丁炔 、 乙酰乙酸乙酯 在 sodium hydride 、 正丁基锂 、 六甲基磷酰三胺 作用下， 以 四氢呋喃 为溶剂， 生成 ethyl 3-oxooct-7-ynoate
  参考文献：
  名称：

  铟催化的ω-炔基-β-酮酸酯的环异构化为6至15元环。

  摘要：

  DOI：

  10.1002/anie.200702928

文献信息

• A Complementary Process to Pauson–Khand-Type Annulation Reactions for the Construction of Fully Substituted Cyclopentenones
  作者：Adam B. Millham、Matthew J. Kier、Robert M. Leon、Rajdip Karmakar、Zachary D. Stempel、Glenn C. Micalizio

  DOI：10.1021/acs.orglett.8b03922

  日期：2019.1.18

  Pauson-Khand annulation is described that is well suited to forging densely substituted/oxygenated cyclopentenone products (including fully substituted variants). The reaction is thought to proceed through a sequence of metallacycle-mediated bond-forming events that engages an internal alkyne and a β-keto ester in an annulation process that forges two C-C bonds. A variant of this annulation process has

  描述了 Pauson-Khand 环化的补充工艺，该工艺非常适合锻造密集取代/氧化的环戊烯酮产品（包括完全取代的变体）。该反应被认为是通过一系列金属环介导的成键事件进行的，该事件使内部炔烃和β-酮酯参与形成两个CC键的环化过程。还建立了这种成环过程的变体，其提供缺乏烯丙基叔醇的脱氧环戊烯酮。
• Synthesis of β-Keto Esters In-Flow and Rapid Access to Substituted Pyrimidines
  作者：Hannah E. Bartrum、David C. Blakemore、Christopher J. Moody、Christopher J. Hayes

  DOI：10.1021/jo101783m

  日期：2010.12.17

  We have developed an in-flow process for the synthesis of beta-keto esters via the BF3 center dot OEt2-catalyzed formal C-H insertion of ethyl diazoacetate into aldehydes. The beta-keto esters were then condensed with a range of amidines to give a variety of 2,6-substituted pyrimidin-4-ols.
• Efficient Formation of Ring Structures Utilizing Multisite Activation by Indium Catalysis
  作者：Yoshimitsu Itoh、Hayato Tsuji、Ken-ichi Yamagata、Kohei Endo、Iku Tanaka、Masaharu Nakamura、Eiichi Nakamura

  DOI：10.1021/ja805657h

  日期：2008.12.17

  Lewis acidic indium(III) salts, in particular In(NTf2)(3), effect the conversion of alpha-(omega'-alkynyl)-beta-ketoesters; and omega-alkynyl-beta-ketoesters to the corresponding cyclic products in a manner known as the Coniaene reaction. This reaction can lead to the creation of five- to fifteen-membered-ring carbocycles and heterocycles in good to excellent yields. The synthetic features of the reaction are a relatively low catalyst loading, as low as 0.01 mol % in the best case, as well as no requirement of solvent for five-membered-ring formation and the requirement of only moderately dilute reaction conditions for medium-sized-ring formation. The high reactivity of indium salts is due to the double activation of the beta-ketoester substrate containing an acetylene function. The indium metal activates the beta-ketoester moiety by the formation of an indium enolate, and this indium metal electrophilically activates the alkyne moiety. Such a strong push-pull activation of the substrate by a single metal circumvents the disadvantage of entropic and enthalpic factors generally associated with the formation of medium- and large-sized rings. The reaction allows the ready formation of a fifteen-membered-ring carbocycle, from which di-muscone has been synthesized.
• Indium-Catalyzed Cycloisomerization of ω-Alkynyl-β-ketoesters into Six- to Fifteen-Membered Rings
  作者：Hayato Tsuji、Ken-ichi Yamagata、Yoshimitsu Itoh、Kohei Endo、Masaharu Nakamura、Eiichi Nakamura

  DOI：10.1002/anie.200702928

  日期：2007.10.22
• Yb(OTf)3-Promoted ZnCl2-Catalyzed Conia-Ene Reaction of Linear β-Alkynic β-Dicarbonyls
  作者：Jin-Heng Li、Yu Liu、Ren-Jie Song

  DOI：10.1055/s-0030-1258213

  日期：2010.11

  An atom-economical and solvent-free ytterbium(III) triflate promoted, zinc(II) chloride catalyzed Conia-ene method has been developed for the construction of five- to six-membered-ring carbocycles. In the presence of zinc(II) chloride and ytterbium(III) triflate, a variety of linear β-alkynic β-keto esters and β-alkynic β-diketones were cyclized under neat conditions in moderate to good yields. It

  已经开发了一种原子经济且无溶剂的三氟甲磺酸（III）促进的氯化锌（II）催化的Conia-ene方法，用于构建五元至六元环的碳环。在氯化锌（II）和三氟甲磺酸（III）的存在下，在纯净条件下，以中等至良好的收率将各种线性的β-链烯基β-酮酸酯和β-链烯基β-二酮环化。值得注意的是，对五或六元环碳环的选择性取决于末端炔烃上的取代基。 氯化锌（II）-三氟甲磺酸（III）-Conia-ene反应-线性β-炔烃β-二羰基-碳环