ethyl 4-(diethoxyphosphoryl)-2-methylbut-2-enoate | 161431-74-9

• 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 4-(diethoxyphosphoryl)-2-methylbut-2-enoate
• 英文别名: 4-(Diethoxyphosphinyl)-2-methyl-2-butenoic acid ethyl ester；ethyl (E)-4-diethoxyphosphoryl-2-methylbut-2-enoate
• CAS: 161431-74-9
• 化学式: C₁₁H₂₁O₅P
• 分子量: 264.259
• InChiKey: UJTQBEHQOLXVAK-CSKARUKUSA-N

物化性质

• 沸点：
  345.3±35.0 °C(Predicted)
• 密度：
  1.083±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  17
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl 4-(diethoxyphosphoryl)-2-methylbut-2-enoate 在 lithium hydroxide 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 35.17h， 生成 (2E,4E)-5-((3S,4S,4aS,5S,6S,7R,8aR)-3,4,4a,5,6,7,8,8a-octahydro-6-(tert-butyldimethylsiloxy)-3,5,7-trimethylnaphthalen-4-yl)-2-methylpenta-2,4-dienoic acid
  参考文献：
  名称：

  Total Synthesis of AMF-26, an Antitumor Agent for Inhibition of the Golgi System, Targeting ADP-Ribosylation Factor 1

  摘要：

  An effective method for the total synthesis of 1 (AMF-26), a potentially promising new anticancer drug that disrupts the Golgi system by inhibiting the ADP-ribosylation factor 1 (Arf1) activation, has been developed for the first time. The construction of the chiral linear precursor (a key to the synthesis) was achieved by the asymmetric aldol reaction followed by the computer-assisted predictive stereoselective intramolecular Diels-Alder reaction. The global antitumor activity of the totally synthetic 1 against a variety of human cancer cells was assessed using a panel of 39 human cancer cell lines (JFCR39), and it was shown that the synthetic 1 strongly inhibited the growth of several cancer cell lines at concentrations of less than 0.04 mu M. Biological assays of novel derivatives, 26 and 31, which have different side-chains at the C-4 positions in the Delta(1,2)-octalin backbone, disclosed the importance of the suitable structure of the side-chain containing conjugated multidouble bonds.

  DOI：

  10.1021/jm301695c
• 作为产物：
  描述：

  diethyl (E)-crotylphosphonate 在 盐酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 ethyl 4-(diethoxyphosphoryl)-2-methylbut-2-enoate
  参考文献：
  名称：

  New and efficient synthesis of (E)-4-diethoxyphosphonyl-2-methyl-2-butenal and of ethyl (E)-4-diethoxyphosphonyl-2-methyl-2-butenoate, important building blocks in retinoid chemistry

  摘要：

  Lithiated anion of diethyl alpha-trimethylsilyl-crotylphosphonate, in-situ generated from readily available diethyl crotylphosphonate, reacts smoothly with ethyl formate or ethyl chloroformate to give the title compounds 1 or 2, respectively, in high isolated yield.

  DOI：

  10.1016/0040-4039(94)02274-f

文献信息

• A DNA‐Encoded Chemical Library Incorporating Elements of Natural Macrocycles
  作者：Cedric J. Stress、Basilius Sauter、Lukas A. Schneider、Timothy Sharpe、Dennis Gillingham

  DOI：10.1002/anie.201902513

  日期：2019.7.8

  Here we show a seven‐step chemical synthesis of a DNA‐encoded macrocycle library (DEML) on DNA. Inspired by polyketide and mixed peptide‐polyketide natural products, the library was designed to incorporate rich backbone diversity. Achieving this diversity, however, comes at the cost of the custom synthesis of bifunctional building block libraries. This study outlines the importance of careful retrosynthetic

  在这里，我们展示了在DNA上进行DNA编码的大环文库（DEML）的七步化学合成。受聚酮化合物和肽-聚酮化合物混合天然产物的启发，该文库旨在整合丰富的骨架多样性。但是，要实现这种多样性，就要以双功能构件块库的定制合成为代价。这项研究概述了在DNA编码文库中仔细进行逆向合成设计的重要性，同时揭示了需要新的DNA合成方法的领域。
• Twelve-Step Asymmetric Synthesis of (−)-Nodulisporic Acid C
  作者：Nicole A. Godfrey、Devon J. Schatz、Sergey V. Pronin

  DOI：10.1021/jacs.8b09965

  日期：2018.10.10

  A short, enantioselective synthesis of (-)-nodulisporic acid C is described. The route features two highly diastereoselective polycyclizations en route to the terpenoid core and the indenopyran fragment and a highly convergent assembly of a challenging indole moiety. Application of this chemistry allows for a 12-step synthesis of the target indoloterpenoid from commercially available material.

  描述了 (-)-nodulisporic acid C 的简短对映选择性合成。该路线具有两个高度非对映选择性的多环化，在通往萜类核心和茚并片段的途中，以及具有挑战性的吲哚部分的高度收敛组装。这种化学方法的应用允许从市售材料中进行 12 步合成目标吲哚萜。
• Highly Regio- and Enantioselective Hydrogenation of Conjugated α-Substituted Dienoic Acids
  作者：Xian Liu、Song Liu、Quanjun Wang、Gang Zhou、Lin Yao、Qin Ouyang、Ru Jiang、Yu Lan、Weiping Chen

  DOI：10.1021/acs.orglett.0c00915

  日期：2020.4.17

  Highly regio- and enantioselective hydrogenation of conjugated α-substituted dienoic acids was realized for the first time using Trifer–Rh complex, providing a straightforward method for the synthesis of chiral α-substituted γ,δ-unsaturated acids. DFT calculations revealed N+H–O hydrogen bonding interaction is formed to stabilize the transition state and the coordination of 4,5-double bond to Rh(III)

  使用Trifer-Rh配合物首次实现了对共轭α-取代二烯酸的高度区域和对映选择性加氢，为合成手性α-取代的γ，δ-不饱和酸提供了一种简单的方法。DFT计算表明，形成N + H–O氢键相互作用可稳定过渡态，并且4,5-双键与Rh（III）中心的配位将促进还原消除过程。该氢化提供了沙比特利前体的克级合成。
• Process for preparing polyenedialdehyde monoacetals
  申请人：——

  公开号：US20030158427A1

  公开（公告）日：2003-08-21

  A process for preparing compounds of the formula I 1 is described and entails converting a compound of the formula II 2 by Wittig or Wittig-Horner reaction into a compound of the formula IV, 3 where appropriate converting the compound of the formula IV by hydrolysis of the acetal function and Wittig or Wittig-Horner reaction into a compound of the formula VI 4 and converting the compound of the formula IV or VI in two stages into the compound of the formula I. The radicals R 1 , R 2 and R 6 and k have the meaning indicated in the description. Novel intermediates are also described.

  描述了一种制备化合物I1的过程，包括通过Wittig或Wittig-Horner反应将化合物II2转化为化合物IV,3，必要时通过水解缩醛基团和Wittig或Wittig-Horner反应将化合物IV转化为化合物VI4，并将化合物IV或VI分两阶段转化为化合物I的过程。基团R1、R2和R6以及k在描述中有所指示。还描述了新的中间体。
• Synthesis of the C19-C34 Segment of Amphidinolide C
  作者：Debendra Mohapatra、Hasibur Rahaman、Mukund Chorghade、Mukund Gurjar

  DOI：10.1055/s-2007-967968

  日期：——

  The synthesis of the C19-C34 segment of amphidinolide C is described. The key steps include the Mioskowski’s Lewis acid catalyzed epoxide opening with the alcohol, ring-closing metathesis, Wittig reaction, and Nozaki-Hiyama-Kishi coupling reaction.

  介绍了蚜虫内酯 C 的 C19-C34 段的合成。关键步骤包括 Mioskowski 的路易斯酸催化环氧化物与醇的开环、闭环偏析、Wittig 反应和 Nozaki-Hiyama-Kishi 偶联反应。