(E)-ethyl 5-methyl-2-oxo-3-hexenoate | 145784-36-7

• 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: (E)-ethyl 5-methyl-2-oxo-3-hexenoate
• 英文别名: ethyl (E)-5-methyl-2-oxohex-3-enoate
• CAS: 145784-36-7
• 化学式: C₉H₁₄O₃
• 分子量: 170.208
• InChiKey: SGJDNSIOBUETNC-AATRIKPKSA-N

物化性质

• 沸点：
  225.6±13.0 °C(Predicted)
• 密度：
  0.991±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 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：

  (E)-ethyl 5-methyl-2-oxo-3-hexenoate 在 正丁基锂 、 L-Selectride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 1.92h， 生成 (E)-(R)-2-Hydroxy-5-methyl-hex-3-enoic acid (1R,2S)-2-phenyl-cyclohexyl ester
  参考文献：
  名称：

  Enantiospecific and diastereoselective synthesis of syn-β-amino-α-hydroxy acids

  摘要：

  The reaction of chiral alpha-hydroxy beta,gamma-unsaturated esters with tosyl isocyanate followed by cyclization of the resulting allylic carbamates with iodine in the presence of sodium carbonate provided trans-4,5-disubstituted 2-oxazolidinone derivatives in a highly diastereoselective manner. The subsequent removal of the iodo group and the protective functionality afforded the syn-beta-amino-alpha-hydroxy acids. Using the reaction sequence, (2R,3S)- and (2S,3R)-3-amino-2-hydroxy acids were synthesized with high enantioselectivity. (C) 1997 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(97)00595-8
• 作为产物：
  描述：

  ethyl 4-methoxy-5-methyl-2-oxohexanoate 在 silica gel 作用下， 以 苯 为溶剂， 反应 5.0h， 生成 (E)-ethyl 5-methyl-2-oxo-3-hexenoate
  参考文献：
  名称：

  A New Synthetic Method for α-Oxo-β,γ-unsaturated Esters

  摘要：

  α-氧代-β,γ-不饱和酯已通过两步法以中等至良好的产率制备，该方法包括先用三氟化硼促进2-(三甲基硅氧基)丙烯酸酯与缩醛的反应，然后在回流苯中用硅胶处理。

  DOI：

  10.1246/bcsj.65.3209

文献信息

• Metal-Free Michael-Addition-Initiated Three-Component Reaction for the Regioselective Synthesis of Highly Functionalized Pyridines: Scope, Mechanistic Investigations and Applications
  作者：Christophe Allais、Frédéric Liéby-Muller、Jean Rodriguez、Thierry Constantieux

  DOI：10.1002/ejoc.201300246

  日期：2013.7

  and completely regioselective three-component synthesis of highly functionalized pyridines from 1,3-dicarbonyl derivatives and Michael acceptors has been achieved. Activated Michael acceptors, that is, β,γ-unsaturated α-oxo carbonyl derivatives, were utilized, allowing substitution at the 4-position and remarkable functional diversity at the 2-position of the pyridine ring. The scope and limitations

  已经实现了由 1,3-二羰基衍生物和迈克尔受体合成高度官能化吡啶的无金属和完全区域选择性的三组分合成。利用活化的迈克尔受体，即 β,γ-不饱和 α-羰基衍生物，允许在吡啶环的 4 位取代和在 2 位显着的功能多样性。公开了这种环境友好的多米诺骨牌反应的范围和局限性，并提供了完整的实验数据，并讨论了机理研究的结果。
• Enantioselective Synthesis of Dihydropyrans. Catalysis of Hetero Diels−Alder Reactions by Bis(oxazoline) Copper(II) Complexes
  作者：David A. Evans、Jeffrey S. Johnson、Edward J. Olhava

  DOI：10.1021/ja992175i

  日期：2000.3.1

  C2-symmetric bis(oxazoline)−Cu(II) complexes 1 and 2 catalyze the inverse electron demand hetero Diels−Alder reaction of α,β-unsaturated carbonyl compounds (heterodiene) with electron-rich olefins (heterodienophile) in high diastereo- and enantioselectivity. α,β-Unsaturated acyl phosphonates and β,γ-unsaturated α-keto esters and amides are effective heterodienes, while enol ethers and sulfides function

  C2-对称双(恶唑啉)-Cu(II)配合物1和2催化α,β-不饱和羰基化合物（杂二烯）与高非对映异构体中的富电子烯烃（亲异二烯体）的反电子需求杂Diels-Alder反应对映选择性。α,β-不饱和酰基膦酸酯和 β,γ-不饱和 α-酮酯和酰胺是有效的杂二烯，而烯醇醚和硫化物则起到亲杂二烯的作用。杂二烯上可能有一系列取代模式：末端烷基、芳基、烷氧基和硫醚取代基都是可以容忍的。通过这种方法对二氢吡喃的对映选择性合成已被证明是直接的：环加成可以用低至 0.2 mol% 的手性催化剂进行，并且很容易以多克规模进行。该反应表现出有利的温度-对映选择性曲线，即使在室温下选择性也超过 90%。采用固体空气稳定催化剂的简单反应方案，方便的反应温度...
• ChiralC2-Symmetric CuII Complexes as Catalysts for Enantioselective Hetero-Diels-Alder Reactions
  作者：David A. Evans、Edward J. Olhava、Jeffrey S. Johnson、Jacob M. Janey

  DOI：10.1002/(sici)1521-3773(19981231)37:24<3372::aid-anie3372>3.0.co;2-k

  日期：1998.12.31

  Air-stable and recyclable, the CuII -(bis)oxazoline complex 1 efficiently catalyzes diastereo- and enantioselective hetero-Diels-Alder reactions between β,γ-unsaturated α-keto acid derivatives 2 and vinyl ethers for the synthesis of substituted dihydropyrans 3 [Eq. (1)]. Results of the crystal structure analysis of 1 in combination with calculations on model compounds indicate the formation of a reactive

  Cu II-（双）恶唑啉络合物1空气稳定且可回收，可有效催化β，γ-不饱和α-酮酸衍生物2和乙烯基醚之间的非对映和对映选择性杂Diels-Alder反应，用于合成取代的二氢吡喃3 [等式 （1）]。1的晶体结构分析结果与对模型化合物的计算相结合，表明通过用螯合底物取代两个H 2 O配体，形成了反应性中间体。X = OEt，N（OMe）Me；R ＝烷基，芳基，烷氧基，硫代苄基。
• Organocatalytic asymmetric conjugate addition of cyclic 1,3-dicarbonyl compounds to β,γ-unsaturated α-ketoesters
  作者：Jin-jia Wang、Jin-hua Lao、Zhi-peng Hu、Rui-Jiong Lu、Shao-zhen Nie、Quan-sheng Du、Ming Yan

  DOI：10.3998/ark.5550190.0011.922

  日期：——

  The conjugate addition of cyclic 1,3-dicarbonyl compounds to β,γ-unsaturated α-keto-esters was studied using a series of chiral bifunctional organocatalysts. Takemoto’s catalyst was found to be most efficient for this transformation. Excellent yields and good enantioselectivities were achieved for a variety of β,γ-unsaturated α-keto-esters and cyclic 1,3-dicarbonyl compounds. A bifunctional catalytic

  使用一系列手性双功能有机催化剂研究了环状 1,3-二羰基化合物与 β,γ-不饱和 α-酮酯的共轭加成。竹本的催化剂被发现对这种转变最有效。各种 β,γ-不饱和 α-酮酯和环状 1,3-二羰基化合物均获得了优异的产率和良好的对映选择性。提出了一种双功能催化机制。该方法为手性香豆素衍生物提供了一条新的不对称合成路线。
• Enantioselective Conjugate Addition of <i>N</i>,<i>N</i>-Dialkylhydrazones to α-Hydroxy Enones
  作者：David Monge、Eloísa Martín-Zamora、Juan Vázquez、Manuel Alcarazo、Eleuterio Álvarez、Rosario Fernández、José M. Lassaletta

  DOI：10.1021/ol071055+

  日期：2007.7.1

  The activation of alpha-hydroxy enones by the Zn(OTf)2/tBuBOX catalyst enables the enantioselective conjugate addition of 1-methyleneaminopyrrolidine as a neutral d1 synthon. Experimental evidence supports a stereochemical model where a triflate ligand controls the geometry of the catalyst-substrate complex by means of a OH-OTf hydrogen bond. The synthesis of beta-cyano acids illustrates the potential

  Zn（OTf）2 / tBuBOX催化剂对α-羟基烯酮的活化使得对映选择性共轭加成1-亚甲基氨基吡咯烷作为中性d1合成子。实验证据支持立体化学模型，其中三氟甲磺酸酯配体通过OH-OTf氢键控制催化剂-底物配合物的几何形状。β-氰基酸的合成说明了该方法的潜力。