5-(苯基甲氧基)-2-戊烯酸乙酯 | 128217-53-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 5-(苯基甲氧基)-2-戊烯酸乙酯
• 英文名称: (E,Z)-methyl 5-(benzyloxy)-2-pentenoate
• 英文别名: Methyl 5-(benzyloxy)pent-2-enoate；methyl 5-phenylmethoxypent-2-enoate
• CAS: 128217-53-8
• 化学式: C₁₃H₁₆O₃
• 分子量: 220.268
• InChiKey: RVALDTQCCVGPIC-UHFFFAOYSA-N

物化性质

• 沸点：
  140 °C(Press: 0.9 Torr)
• 密度：
  1.057±0.06 g/cm3(Predicted)
• 溶解度：
  可溶于二氯甲烷、乙酸乙酯

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 可旋转键数：
  7
• 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：

  5-(苯基甲氧基)-2-戊烯酸乙酯 在 甲基叔丁基醚 、 palladium 10% on activated carbon 、 氢气 、 (±)-2,2 '-二(二-对甲苯基膦)-1,1 '-联萘 、 copper(I) bromide 作用下， 以 乙醚 、 乙醇 为溶剂， 反应 8.75h， 生成 (S)-4-methyltetrahydro-2H-pyran-2-one
  参考文献：
  名称：

  立体选择性合成两种高效的5-oxo-ETE受体拮抗剂

  摘要：

  描述了具有高水平对映体纯度的高效5-oxo-ETE受体拮抗剂5a和6a的对映选择性合成。这项工作的主要特点是简单有效地合成对映体比率为S / R：98.4 / 1.6的双官能化3-（S）-甲基戊二酸单甲酯（24）。我们研究了MeMgBr在CuBr /（S）-Tol-BINAP系统催化下的5-苯甲氧基-戊-2-烯酸甲酯（23）的不对称共轭加成反应，并优化了反应条件的区域选择性和高对映选择性。

  DOI：

  10.1016/j.tetlet.2015.10.097
• 作为产物：
  描述：

  3-苄氧基-1-丙醇 在 草酰氯 、 三乙胺 作用下， 以 二甲基亚砜 为溶剂， 生成 5-(苯基甲氧基)-2-戊烯酸乙酯
  参考文献：
  名称：

  手性锡(II)烯醇盐的高度立体选择性醛醇型反应。(±)-噻那霉素的正式全合成

  摘要：

  在由 3-氨基取代的丁酰基噻唑烷-2-硫酮生成的锡 (II) 烯醇化物的羟醛型反应中实现了高效的内部手性诱导。该反应成功应用于(±)-硫霉素的正式全合成。

  DOI：

  10.1246/cl.1986.637

文献信息

• Radical substitution with azide: TMSN₃–PhI(OAc)₂as a substitute of IN₃
  作者：Christian Marcus Pedersen、Lavinia Georgeta Marinescu、Mikael Bols

  DOI：10.1039/b500037h

  日期：——

  TMSN3 and PhI(OAc)2 were found to promote high-yield azide substitution of ethers, aldehydes and benzal acetals. The reaction is fast and occurs at zero to ambient temperature in acetonitrile. However, it is essential for the reaction that TMSN3 is added subsequent to the mixture of PhI(OAc)2 and the substrate. A primary deuterium kinetic isotope effect was found for the azidonation of benzyl ethers

  发现TMSN3和PhI（OAc）2可以促进醚，醛和苯甲醛缩醛的高产率叠氮化物取代。该反应是快速的，并且在乙腈中于零至环境温度下发生。但是，对于反应而言必不可少的是，在PhI（OAc）2和底物的混合物之后添加TMSN3。在用TMSN3-PhI（OAc）2和IN3进行苄基醚的叠氮反应中​​，发现了主要的氘动力学同位素效应。该反应的哈米特自由能关系研究也显示与sigma +常数具有良好的相关性，对于TMSN3-PhI（OAc）2，rho值为-0.47，对于IN3，rho值为-0.39。在此基础上，提出了反应的根本机理。
• HIGHLY STEREOSELECTIVE ALDOL-TYPE REACTION OF CHIRAL TIN(II) ENOLATE. FORMAL TOTAL SYNTHESIS OF (±)-THIENAMYCIN
  作者：Nobuharu Iwasawa、Teruaki Mukaiyama

  DOI：10.1246/cl.1986.637

  日期：1986.4.5

  induction is achieved in the aldol-type reaction of tin(II) enolate generated from 3-amino-substituted butanoylthiazolidine-2-thione. This reaction is successfully applied to the formal total synthesis of (±)-thienamycin.

  在由 3-氨基取代的丁酰基噻唑烷-2-硫酮生成的锡 (II) 烯醇化物的羟醛型反应中实现了高效的内部手性诱导。该反应成功应用于(±)-硫霉素的正式全合成。
• A Simple Route to .alpha.-Substituted-.beta.-Amino Ester Precursors of Carbapenem Antibiotics
  作者：Patrick Perlmutter、Mark Tabone

  DOI：10.1021/jo00125a043

  日期：1995.10

  A three-step process is presented for the preparation of alpha-substituted-beta-amino esters which can serve as precursors to a key intermediate in carbapenem synthesis. The pivotal reaction in this sequence involves a highly diastereoselective conjugate addition reaction. Two series of alkenoates bearing a stereogenic substituent attached to C2 were prepared and their conjugate addition reactions with benzylamine studied under several different sets of conditions. Conjugate addition of benzylamine to alkenoates 7a and 7d, in methanol at room temperature, gave adducts 8a and Sd with virtually complete anti-diastereoselectivity. These two beta-amino esters bear the correct relative stereochemistry and side chain to serve as precursors for carbapenem antibiotic synthetic intermediates. The role of the allylic substituents of the alkenoates 7a-e in determining the stereochemical outcome of these additions is discussed. These conjugate additions were explored further by the preparation and conjugate addition reactions of the alpha,beta-disubstituted alkenoates 15a and 15b. It was found that the presence of a beta-substituent led to a dramatic reduction in yield although the same anti-diastereoselectivity was maintained. The relative stereochemistry of the adducts was established by examination of the relevant coupling constants in the H-1 NMR spectra of their tetrahydro-1,3-oxazine derivatives.
• Gold-Catalyzed Formal Hexadehydro-Diels–Alder/Carboalkoxylation Reaction Cascades
  作者：Hong-Fa Wang、Lin-Na Guo、Zhi-Bo Fan、Tian-Hua Tang、Weiwei Zi

  DOI：10.1021/acs.orglett.1c00581

  日期：2021.4.2
• Stereoselective synthesis of two highly potent 5-oxo-ETE receptor antagonists
  作者：Chintam Nagendra Reddy、Qiuji Ye、Shishir Chourey、Sylvie Gravel、William S. Powell、Joshua Rokach

  DOI：10.1016/j.tetlet.2015.10.097

  日期：2015.12

  Enantioselective synthesis of highly potent 5-oxo-ETE receptor antagonists 5a and 6a with a high level of enantiomeric purity is described. The main feature of this work is the simple and efficient synthesis of the bi-functionalized 3-(S)-methyl-pentanedioic acid monomethyl ester (24) with the enantiomeric ratio of S/R:98.4/1.6. We investigated the asymmetric conjugate addition of MeMgBr to 5-Benzyloxy-pent-2-enoic

  描述了具有高水平对映体纯度的高效5-oxo-ETE受体拮抗剂5a和6a的对映选择性合成。这项工作的主要特点是简单有效地合成对映体比率为S / R：98.4 / 1.6的双官能化3-（S）-甲基戊二酸单甲酯（24）。我们研究了MeMgBr在CuBr /（S）-Tol-BINAP系统催化下的5-苯甲氧基-戊-2-烯酸甲酯（23）的不对称共轭加成反应，并优化了反应条件的区域选择性和高对映选择性。