ethyl (E)-6-phenylhex-2-en-5-ynoate | 266325-23-9

• 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)-6-phenylhex-2-en-5-ynoate
• 英文别名: ethyl 6-phenylhex-5-yn-(2E)-enoate；ethyl 6-phenylhex-5-yn-2(E)-enoate
• CAS: 266325-23-9
• 化学式: C₁₄H₁₄O₂
• 分子量: 214.264
• InChiKey: XGRGKSCQCGPMDK-XYOKQWHBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.21
• 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)-6-phenylhex-2-en-5-ynoate 以 N,N-二甲基甲酰胺 为溶剂， 以62%的产率得到ethyl 6-phenylhex-5-yn-3(E)-enoate
  参考文献：
  名称：

  Unusual Regioselectivity of Pd(0)-Catalyzed Coupling Reaction of Electron-Deficient Alkenyl Halides with Allenic/Propargylic Zinc Reagents. Highly Selective Synthesis of 6-Phenylhex-5-yn-2(or 3)-enoates/Enitrile and 4-Phenyl-6-substituted-hexa-2,4,5-trienoates

  摘要：

  The Pd(0)-catalyzed coupling reaction of electron-deficient alkenyl halides with the organozinc formed by the subsequent treatment of 1-phenylalk-1-yne with n-BuLi and ZnBr2 with or without a catalytic amount of HgCl2 was studied. Both the allene-formation- and the alkyne-formation-type coupling reactions were observed with high regio- and stereoselectivity: the reaction of 1-phenylprop-1-yne afforded 6-phenylhex-5-yn-2(or 3)-enoates and -enitriles, while the reaction of 1-phenylhex-1-yne formed 4-phenyl-6-substituted-hexa-2,4,5-trienoates. A plausible explanation for the regioselectivity was discussed. The double bonds in 6-phenylhex-5-yn-2-enoates were prone to migrate to the position conjugated with the carbon-carbon triple bonds to form 6-phenylhex-5-yn-3-enoates at higher temperature. The migration did not occur in absence of an excess amount of allenic/propargylic zinc reagent or at low temperature.

  DOI：

  10.1021/jo991243g
• 作为产物：
  描述：

  1-苯基-1-丙炔 、 ethyl (E)-3-iodopropenoate 在 正丁基锂 、 zinc dibromide 、 四(三苯基膦)钯 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.67h， 以76%的产率得到ethyl (E)-6-phenylhex-2-en-5-ynoate
  参考文献：
  名称：

  Unusual Regioselectivity of Pd(0)-Catalyzed Coupling Reaction of Electron-Deficient Alkenyl Halides with Allenic/Propargylic Zinc Reagents. Highly Selective Synthesis of 6-Phenylhex-5-yn-2(or 3)-enoates/Enitrile and 4-Phenyl-6-substituted-hexa-2,4,5-trienoates

  摘要：

  The Pd(0)-catalyzed coupling reaction of electron-deficient alkenyl halides with the organozinc formed by the subsequent treatment of 1-phenylalk-1-yne with n-BuLi and ZnBr2 with or without a catalytic amount of HgCl2 was studied. Both the allene-formation- and the alkyne-formation-type coupling reactions were observed with high regio- and stereoselectivity: the reaction of 1-phenylprop-1-yne afforded 6-phenylhex-5-yn-2(or 3)-enoates and -enitriles, while the reaction of 1-phenylhex-1-yne formed 4-phenyl-6-substituted-hexa-2,4,5-trienoates. A plausible explanation for the regioselectivity was discussed. The double bonds in 6-phenylhex-5-yn-2-enoates were prone to migrate to the position conjugated with the carbon-carbon triple bonds to form 6-phenylhex-5-yn-3-enoates at higher temperature. The migration did not occur in absence of an excess amount of allenic/propargylic zinc reagent or at low temperature.

  DOI：

  10.1021/jo991243g

文献信息

• Tuning of Regioselectivity in the Coupling Reaction Involving Allenic/Propargylic Palladium Species
  作者：Shengming Ma、Aibin Zhang

  DOI：10.1021/jo0111098

  日期：2002.4.1

  Two different types of coupling patterns for the Pd(0)-catalyzed coupling reaction of allenic/propargylic zinc reagents with organic halides or propargylic carbonates (acetate) with the corresponding organometallic reagents were observed. After studying the controlling factors on the regioselectivity of this reaction, we demonstrated that the steric hindrance of both reactants and the types of organic

  观察到两种不同类型的偶联模式，用于Pd（0）催化的烯丙基/炔丙基锌试剂与有机卤化物或炔丙基碳酸酯（乙酸盐）与相应的有机金属试剂的偶联反应。在研究了该反应的区域选择性的控制因素后，我们证明了两种反应物的位阻和有机卤化物的类型决定了该偶联反应的区域选择性。通过精细选择底物，可以调节区域选择性。基于这些结果，已经开发出用于高度区域和立体选择性地合成6-取代的6--5-己-2-烯酸酯和4，6-二烷基六-2,4,5-三烯酸酯的新方法。
• Reactivity of Stabilized Vinyldiazo Compounds toward Alkenyl- and Alkynylsilanes under Gold Catalysis: Regio- and Stereoselective Synthesis of Skipped Dienes and Enynes
  作者：Olaya Bernardo、Kota Yamamoto、Israel Fernández、Luis A. López

  DOI：10.1021/acs.orglett.1c01381

  日期：2021.6.4

  the gold-catalyzed reaction of vinyldiazo compounds and alkenylsilanes to produce skipped dienes, which are common structural motifs in an array of bioactive compounds. This carbon–carbon bond-forming transformation proceeds with complete regio- and stereoselectivity with the silyl group serving as a regio- and stereocontrolling element. Likewise, the use of alkynylsilanes as reaction partners yielded

  我们报告了乙烯基重氮化合物和烯基硅烷的金催化反应生成跳过的二烯，这是一系列生物活性化合物中常见的结构基序。这种碳-碳键形成转化以完全的区域和立体选择性进行，甲硅烷基作为区域和立体控制元素。同样，使用炔基硅烷作为反应伙伴会产生由 C(sp)-C(sp 3 ) 偶联产生的跳过的烯炔。机械实验和 DFT 研究为逐步机制提供了支持。
• Unusual Regioselectivity of Pd(0)-Catalyzed Coupling Reaction of Electron-Deficient Alkenyl Halides with Allenic/Propargylic Zinc Reagents. Highly Selective Synthesis of 6-Phenylhex-5-yn-2(or 3)-enoates/Enitrile and 4-Phenyl-6-substituted-hexa-2,4,5-trienoates
  作者：Shengming Ma、Aibin Zhang、Yihua Yu、Wei Xia

  DOI：10.1021/jo991243g

  日期：2000.4.1

  The Pd(0)-catalyzed coupling reaction of electron-deficient alkenyl halides with the organozinc formed by the subsequent treatment of 1-phenylalk-1-yne with n-BuLi and ZnBr2 with or without a catalytic amount of HgCl2 was studied. Both the allene-formation- and the alkyne-formation-type coupling reactions were observed with high regio- and stereoselectivity: the reaction of 1-phenylprop-1-yne afforded 6-phenylhex-5-yn-2(or 3)-enoates and -enitriles, while the reaction of 1-phenylhex-1-yne formed 4-phenyl-6-substituted-hexa-2,4,5-trienoates. A plausible explanation for the regioselectivity was discussed. The double bonds in 6-phenylhex-5-yn-2-enoates were prone to migrate to the position conjugated with the carbon-carbon triple bonds to form 6-phenylhex-5-yn-3-enoates at higher temperature. The migration did not occur in absence of an excess amount of allenic/propargylic zinc reagent or at low temperature.