ethyl (E)-4,4-ethylenedioxy-3-methylbut-2-enoate | 65527-87-9

• 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 (E)-4,4-ethylenedioxy-3-methylbut-2-enoate
• 英文别名: ethyl (E)-3-(1,3-dioxolan-2-yl)but-2-enoate
• CAS: 65527-87-9
• 化学式: C₉H₁₄O₄
• 分子量: 186.208
• InChiKey: JJZPYZBNESYWRH-VOTSOKGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl (E)-4,4-ethylenedioxy-3-methylbut-2-enoate 在 咪唑 、 六甲基磷酰三胺 、 lithium aluminium tetrahydride 、 四(三苯基膦)钯 、 氢氧化铊(Ⅰ) 、 四丁基氟化铵 、 水 、 sodium hexamethyldisilazane 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 乙醚 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 8.25h， 生成 (2E,4Z,6E,8E)-3-Methyl-9-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-2,4,6,8-tetraen-1-ol
  参考文献：
  名称：

  Stereospecific synthesis of 9-demethylretinoids via palladium-catalyzed vinylboronic acid-vinyl iodide cross coupling

  摘要：

  A stereospecific synthesis of 9-demethylretinoids with either trans or 11-cis geometries, based on the thallium-accelerated palladium-catalyzed cross-coupling reactions of an (E)-1-alkenylboronic acid and (E) or (Z)-alkenyl iodides, is described.

  DOI：

  10.1016/s0040-4039(00)60044-8
• 作为产物：
  描述：

  3-甲酰基-2-丁烯酸乙酯 、 乙二醇 在 4-甲基苯磺酸吡啶 作用下， 以89%的产率得到ethyl (E)-4,4-ethylenedioxy-3-methylbut-2-enoate
  参考文献：
  名称：

  Didehydrofarnesyl diphosphate: an intrinsically fluorescent inhibitor of protein farnesyltransferase

  摘要：

  Didehydrofarnesyl diphosphate (DeltaDeltaFPP), a fluorescent pentaene analogue of farnesyl diphosphate (FPP), was synthesized using stereoselective Wittig reactions. Although DeltaDeltaFPP was not an alternative substrate for yeast protein farnesyltransferase (FTase), the fluorescent analogue was a potent competitive inhibitor with a K-i value of 8.8 muM (K-m (FPP) = 27 muM). (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2004.02.077

文献信息

• γ-Allenyl Allyl Benzothiazole Sulfonyl Anions Undergo<i>cis</i>-Selective (Sylvestre) Julia Olefinations
  作者：Angel R. de Lera、Belén Vaz、Rosana Alvarez、José A. Souto

  DOI：10.1055/s-2004-837214

  日期：——

  γ-Allenyl allyl benzothiazolyl sulfones 8 and ent-8 provided allenyl trienes and polyenes with cis-selectivities ranging from 71:29 to 100:0 upon condensation (NaHMDS, THF, -78 °C to 25 °C) with a variety of unsaturated aldehydes.

  γ-烯丙基苯并噻唑基砜 8 和 ent-8 提供了顺式选择性范围为 71:29 至 100:0 的丙二烯基三烯和多烯（NaHMDS、THF、-78 °C 至 25 °C）与各种不饱和醛类。
• Boron-enabled geometric isomerization of alkenes via selective energy-transfer catalysis
  作者：John J. Molloy、Michael Schäfer、Max Wienhold、Tobias Morack、Constantin G. Daniliuc、Ryan Gilmour

  DOI：10.1126/science.abb7235

  日期：2020.7.17

  Isomerization-based strategies to enable the stereodivergent construction of complex polyenes from geometrically defined alkene linchpins remain conspicuously underdeveloped. Mitigating the thermodynamic constraints inherent to isomerization is further frustrated by the considerations of atom efficiency in idealized low–molecular weight precursors. In this work, we report a general ambiphilic C3 scaffold that can

  基于异构化的策略，能够使由几何定义的烯烃关键构形的复杂多烯立体发散地构建仍然明显欠发达。理想化的低分子量前体中对原子效率的考虑，进一步减轻了异构化固有的热力学约束。在这项工作中，我们报告了一个通用的C 3支架，该支架可以异构化并双向延伸。基于高效的三重态能量转移，β-硼丙烯酸酯的选择性异构化取决于硼p轨道在底物发色团中的参与。C（sp 2的旋转）–产品中90°的B键使重新励磁效率低下并赋予方向性。这种微妙的立体电子门控机制可实现清晰定义的视黄酸衍生物的立体控制合成。
• The suzuki reaction in stereocontrolled polyene synthesis: Retinol (vitamin A), its 9- and/or 13-demethyl analogs, and related 9-demethyl-dihydroretinoids
  作者：Alicia Torrado、Beatriz Iglesias、Susana López、Angel R. de Lera

  DOI：10.1016/0040-4020(94)01108-c

  日期：1995.2

  A new synthesis of retinol (vitamin A) and 9- and/or 13-demethylretinols, with essentially complete control of regio- and stereochemistry, is described which is based on the thallium-accelerated, palladium-catalyzed cross-coupling reactions of (E)-1-alkenylboronic acids and (E)-1-alkenyl iodides (Suzuki reaction). The procedure has also been extended to the stereocontrolled synthesis of a series of 9-demethyl-dihydroretinoids of potential biological interest.
• Didehydrofarnesyl diphosphate: an intrinsically fluorescent inhibitor of protein farnesyltransferase
  作者：Xiao-hui Liu、Glenn D. Prestwich

  DOI：10.1016/j.bmcl.2004.02.077

  日期：2004.5

  Didehydrofarnesyl diphosphate (DeltaDeltaFPP), a fluorescent pentaene analogue of farnesyl diphosphate (FPP), was synthesized using stereoselective Wittig reactions. Although DeltaDeltaFPP was not an alternative substrate for yeast protein farnesyltransferase (FTase), the fluorescent analogue was a potent competitive inhibitor with a K-i value of 8.8 muM (K-m (FPP) = 27 muM). (C) 2004 Elsevier Ltd. All rights reserved.
• Stereospecific synthesis of 9-demethylretinoids via palladium-catalyzed vinylboronic acid-vinyl iodide cross coupling
  作者：Angel R. de Lera、Alicia Torrado、Beatriz Iglesias、Susana López

  DOI：10.1016/s0040-4039(00)60044-8

  日期：1992.10

  A stereospecific synthesis of 9-demethylretinoids with either trans or 11-cis geometries, based on the thallium-accelerated palladium-catalyzed cross-coupling reactions of an (E)-1-alkenylboronic acid and (E) or (Z)-alkenyl iodides, is described.