(E)-4-(4'-methoxyphenyl)but-3-en-2-yl acetate | 99512-11-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (E)-4-(4'-methoxyphenyl)but-3-en-2-yl acetate
• 英文别名: (E)-4-(4-methoxyphenyl)but-3-en-2-yl acetate；[(E)-4-(4-methoxyphenyl)but-3-en-2-yl] acetate
• CAS: 99512-11-5
• 化学式: C₁₃H₁₆O₃
• 分子量: 220.268
• InChiKey: FSXWBUZBQJPOBF-SNAWJCMRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-4-(4'-methoxyphenyl)but-3-en-2-yl acetate 在 fac-tris(2-phenylpyridinato-N,C2')iridium(III) 、 四(三苯基膦)钯 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 16.0h， 生成 (Z)-4-(4-(4-methoxyphenyl)but-3-en-2-yl)morpholine
  参考文献：
  名称：

  Facile Synthesis of Z-Alkenes via Uphill Catalysis

  摘要：

  Catalytic access to thermodynamically less stable Z-alkenes has recently received considerable attention. These approaches have relied upon kinetic control of the reaction to arrive at the thermodynamically less stable geometrical isomer. Herein, we present an orthogonal approach which proceeds via photochemically catalyzed isomerization of the thermodynamic E-alkene to the less stable Z-isomer which occurs via a photochemical pumping mechanism. We consider two potential mechanisms. Importantly, the reaction conditions are mild, tolerant, and operationally simple and will be easily implemented.

  DOI：

  10.1021/ja5019749
• 作为产物：
  描述：

  4-甲氧基苯甲醛 在 甲醇 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 三乙胺 、 sodium hydroxide 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 17.0h， 生成 (E)-4-(4'-methoxyphenyl)but-3-en-2-yl acetate
  参考文献：
  名称：

  Facile Synthesis of Z-Alkenes via Uphill Catalysis

  摘要：

  Catalytic access to thermodynamically less stable Z-alkenes has recently received considerable attention. These approaches have relied upon kinetic control of the reaction to arrive at the thermodynamically less stable geometrical isomer. Herein, we present an orthogonal approach which proceeds via photochemically catalyzed isomerization of the thermodynamic E-alkene to the less stable Z-isomer which occurs via a photochemical pumping mechanism. We consider two potential mechanisms. Importantly, the reaction conditions are mild, tolerant, and operationally simple and will be easily implemented.

  DOI：

  10.1021/ja5019749

文献信息

• Highly Enantioselective Synthesis of 3-Substituted Furanones by Palladium-Catalyzed Kinetic Resolution of Unsymmetrical Allyl Acetates
  作者：Bin Mao、Yining Ji、Martín Fañanás-Mastral、Giuseppe Caroli、Auke Meetsma、Ben L. Feringa

  DOI：10.1002/anie.201109075

  日期：2012.3.26

  near‐perfect Pd‐catalyzed kinetic resolution of 1,3‐disubstituted unsymmetrical allylic acetates uses silyl enol ethers as nucleophiles to access the important 3‐substituted‐furanone scaffold (see scheme; DACH=diaminocyclohexyl, dba=dibenzylideneacetone). The reaction proceeds under mild conditions and provides the desired products with excellent chemo‐, regio‐, and enantioselectivity.

  解决问题：1,3-二取代的不对称烯丙基乙酸酯的Pd催化动力学拆分接近完美，使用甲硅烷基烯醇醚作为亲核试剂来访问重要的3-取代的呋喃酮骨架（请参见方案; DACH =二氨基环己基，dba =二苄叉基丙酮） 。反应在温和的条件下进行，可提供具有优异的化学，区域和对映选择性的所需产物。
• Radical reactions in esters with alkoxy functionality chemistry an unusual alcohol moiety hydrogen abstraction
  作者：Ming-Chung Yan、Yeong-Jiunn Jang、Jhenyi Wu、Yung-Feng Lin、Ching-Fa Yao

  DOI：10.1016/j.tetlet.2004.02.158

  日期：2004.4

  Various geometrically pure (E)-alkenes have been synthesized by radical substitution of alcohol moieties generated via hydrogen abstraction within ethyl esters. These reactions occurred with high regioselectivity and gave a new access to 1-methyl-3-aryl-allyl esters.

  通过自由基取代由乙基酯内的氢提取产生的醇部分，已经合成了各种几何上纯净的（E）-烯烃。这些反应具有很高的区域选择性，使人们获得了1-甲基-3-芳基-烯丙基酯的新途径。
• Palladium-catalyzed regio- and diastereo-selective allylic alkylation using 2-(diphenylphosphino)benzoic acid: construction of vicinal quaternary and tertiary carbon centers
  作者：Motoi Kawatsura、Daiji Ikeda、Yuji Komatsu、Kana Mitani、Takeshi Tanaka、Junichi Uenishi

  DOI：10.1016/j.tet.2007.06.025

  日期：2007.9

  The palladium-catalyzed regio- and diastereo-selective allylic alkylation of allyl acetates with carbon nucleophiles occurred. The stereochemistry was highly controlled by the palladium catalyst with 2-(diphenylphosphino)benzoic acid as the ligand, and vicinal quaternary and tertiary carbon centers were constructed.

  发生了钯烯丙基乙酸烯丙基酯与碳亲核试剂的区域和非对映选择性烯丙基烷基化反应。用2-（二苯基膦基）苯甲酸作为配体的钯催化剂对立体化学进行了高度控制，并建立了相邻的季碳和叔碳中心。
• Chemoenzymatic Synthesis of trans-β-Aryl-δ-hydroxy-γ-lactones and Enzymatic Kinetic Resolution of Their Racemic Mixtures
  作者：Andrzej Skrobiszewski、Witold Gładkowski、Gabriela Maciejewska、Czesław Wawrzeńczyk

  DOI：10.3390/molecules21111552

  日期：——

  m-chloroperbenzoic acid (m-CPBA). An alternative method for the production of optically active trans-β-aryl-δ-hydroxy-γ-lactones 5a–d was lipase-catalyzed kinetic resolution of their racemic mixtures by transesterification with vinyl propionate as the acyl donor. The most efficient enzyme in the screening procedure was lipase B from Candida antarctica. Its application on a preparative scale after 6 h afforded unreacted

  开发了两种新颖方便的途径来获得对映异构体富集的反式-β-芳基-δ-羟基-γ-内酯 5a-d，具有潜在的拒食和抗癌活性。在第一种方法中，从衍生自酶分解烯丙醇 1a-d 的 γ,δ-不饱和酯 4a-d 的相应对映体开始，羟基内酯 5a-d 的两种对映体都以高对映体过量（73%-97%）合成。基于在间氯过苯甲酸 (m-CPBA) 存在下酯 4a-d 的酸性内酯化机制，对合成化合物的立体中心的构型进行了分配。生产光学活性反式-β-芳基-δ-羟基-γ-内酯 5a-d 的另一种方法是脂肪酶催化的外消旋混合物的动力学拆分，通过与丙酸乙烯酯作为酰基供体进行酯交换。筛选程序中最有效的酶是来自南极念珠菌的脂肪酶 B。它在 6 小时后以制备规模应用得到未反应的 (+)-(4S,5R,6S)-羟基内酯 5a-d 和 (+)-(4R,5S,6R)-丙酸酯 6a-d，其中大部分具有高对映体过量 (92%–98%)。内酯
• Free and Immobilized Lecitase™ Ultra as the Biocatalyst in the Kinetic Resolution of (E)-4-Arylbut-3-en-2-yl Esters
  作者：Aleksandra Leśniarek、Anna Chojnacka、Radosław Drozd、Magdalena Szymańska、Witold Gładkowski

  DOI：10.3390/molecules25051067

  日期：——

  chain length was investigated for the enantioselective hydrolysis of racemic 4-arylbut-3-en-2-yl esters using Lecitase™ Ultra (LU). Immobilized preparations of the Lecitase™ Ultra enzyme had significantly higher activity and enantioselectivity than the free enzyme, particularly for 4-phenylbut-3-en-2-yl butyrate as the substrate. Moreover, the kinetic resolution with the immobilized enzyme was achieved

  使用 Lecitase™ Ultra (LU) 研究了缓冲液类型、共溶剂类型和酰基链长度对外消旋 4-芳基丁-3-烯-2-基酯的对映选择性水解的影响。Lecitase™ Ultra 酶的固定化制剂比游离酶具有显着更高的活性和对映选择性，特别是对于作为底物的 4-phenylbut-3-en-2-yl butyrate。此外，固定化酶的动力学分辨率在更短的时间内（24-48 小时）实现。Lecitase™ Ultra，固定在溴化氰活化的琼脂糖上，特别有效，在以丙酮为共溶剂的磷酸盐缓冲液 (pH 7.2) 中反应 24 小时后，产生 (R)-醇和未反应的 (S)-具有良好到极好的对映体过量（ee 90-99%）的酯。