ethyl 2,3-dimethyl-2-methylcarbonyl-4-phenyl-3(E)-butenoate | 1042096-57-0

• 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 2,3-dimethyl-2-methylcarbonyl-4-phenyl-3(E)-butenoate
• 英文别名: (E)-ethyl 2-acetyl-2,3-dimethyl-4-phenylbut-3-enoate；ethyl 2-acetyl-2,3-dimethyl-4-phenyl-3(E)-butenoate；ethyl (E)-2-acetyl-2,3-dimethyl-4-phenylbut-3-enoate
• CAS: 1042096-57-0
• 化学式: C₁₆H₂₀O₃
• 分子量: 260.333
• InChiKey: AEVDUIVQSQTTQX-VAWYXSNFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-甲基乙酰乙酸乙酯 、 (Z)-2-fluoro-3-phenylallyl acetate 在 三乙基硅烷 、 2,2'-联吡啶 、 bis(η3-allyl-μ-chloropalladium(II)) 、 silver trifluoromethanesulfonate 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 1,2-二氯乙烷 为溶剂， 反应 12.0h， 以46%的产率得到ethyl 2,3-dimethyl-2-methylcarbonyl-4-phenyl-3(E)-butenoate
  参考文献：
  名称：

  2-氟烯丙基乙酸酯的钯催化区域选择性加氢烷基化：乙烯基丙二酸酯衍生物的合成

  摘要：

  开发了钯催化的乙酸烯丙酯与丙二酸阴离子和氢化物的加氢烷基化反应。该反应通过 C-F 键活化进行，并通过与碳亲核试剂和氢化物的区域选择性取代提供乙烯基丙二酸酯衍生物。

  DOI：

  10.1055/s-0034-1380747

文献信息

• Ferric Chloride Hexahydrate-Catalyzed Highly Regio- and Stereoselective Conjugate Addition Reaction of 2,3-Allenoates with Grignard Reagents: An Efficient Synthesis of β,γ-Alkenoates
  作者：Guobi Chai、Zhan Lu、Chunling Fu、Shengming Ma

  DOI：10.1002/adsc.200900091

  日期：2009.8

  Ferric chloride hexahydrate was shown to be an efficient catalyst for the conjugate addition of 2,3-allenoates with alkyl-, aryl-, or vinyl-Grignard reagents to synthesize polysubstituted β,γ-unsaturated alkenoates with high regio- and stereoselectivity. The in situ formed magnesium dienolate may readily react with different electrophilic reagents under different reaction conditions with or without

  六水合氯化铁被证明是2,3-烯丙基酸酯与烷基，芳基或乙烯基格氏试剂共轭加成以合成具有高区域和立体选择性的多取代的β，γ-不饱和烯酸酯的有效催化剂。在原位形成二烯醇镁可以容易地与具有或不具有催化剂不同的反应条件下不同亲电试剂反应以构建在酯基团的α位和碳-碳双键的stereocontrollable保留烯丙基季碳。
• CuCl-catalyzed stereoselective conjugate addition of Grignard reagents to 2,3-allenoates
  作者：Jian He、Zhan Lu、Guobi Chai、Chunling Fu、Shengming Ma

  DOI：10.1016/j.tet.2012.01.027

  日期：2012.3

  CuCl was found to be an efficient catalyst for the conjugate addition of 2,3-allenoates with Grignard reagents to synthesize poly-substituted β,γ-unsaturated alkenoates with high stereoselectivity in good to excellent yields. Primary, secondary, and tertiary alkyl, vinyl or phenyl Grignard reagents may all be used.

  发现CuCl是2,3-脲基酸酯与Grignard试剂共轭加成以高立体选择性，高产率到优良产率合成多取代的β，γ-不饱和链烯酸酯的有效催化剂。伯，仲和叔烷基，乙烯基或苯基格氏试剂均可使用。
• Controllable Highly Stereoselective Reaction of <i>in situ</i> Generated Magnesium Dienolate Intermediates with Different Electrophiles
  作者：Zhan Lu、Guobi Chai、Xiaobing Zhang、Shengming Ma

  DOI：10.1021/ol8012815

  日期：2008.8.21

  In this paper, we have described an efficient controllable stereoselective a-acylation and -allylation reaction of the magnesium dienolate intermediates generated in situ from the Fe(III)-catalyzed reaction between 2,3-allenoates and Grignard reagents with different electrophiles to afford 2-acylated or allylated 3(Z)- or (E)-alkenoates depending on the nature of the electrophiles and reaction conditions. The distinct stereoselectivity may be caused by the isomerization of metallic Z-1,3-dienoate to E-1,3-dienoate via the intermediacy of anti-allylic MgCl and syn-metallic species.