dimethyl (3-methyl-2-butenyl)propanedioate | 43219-18-7

• 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: dimethyl (3-methyl-2-butenyl)propanedioate
• 英文别名: dimethyl 2-(3-methylbut-2-en-1-yl)malonate；dimethyl prenylmalonate；dimethyl 2-(3-methylbut-2-enyl)malonate；Dimethyl(3,3-dimethylallyl)malonate；dimethyl 2-(3-methylbut-2-enyl)propanedioate
• CAS: 43219-18-7
• 化学式: C₁₀H₁₆O₄
• 分子量: 200.235
• InChiKey: RSBCGIJLSBECTL-UHFFFAOYSA-N

物化性质

• 沸点：
  210.8±20.0 °C(Predicted)
• 密度：
  1.030±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  dimethyl (3-methyl-2-butenyl)propanedioate 在 potassium hydroxide 作用下， 以 甲醇 、 水 为溶剂， 反应 1.0h， 以83%的产率得到2-(3-甲基丁-2-烯基)丙二酸
  参考文献：
  名称：

  Bishomoisoprenoid triazole bisphosphonates as inhibitors of geranylgeranyl diphosphate synthase

  摘要：

  Protein geranylgeranylation reactions are dependent on the availability of geranylgeranyl diphosphate (GGDP), which serves as the isoprenoid donor. Inhibition of GGDP synthase (GGDPS) is of interest from a drug development perspective as GGDPS inhibition results in impaired protein geranylgeranylation, which in multiple myeloma, disrupts monoclonal protein trafficking and induces apoptosis. We have recently reported a series of isoprenoid triazole bisphosphonates and have demonstrated that a 3:1 mixture of homogeranyl and homoneryl isomers potently, and in a synergistic manner, inhibits GGDPS. We now present the synthesis and biological evaluation of a novel series of bishomoisoprenoid triazoles which furthers our understanding of the structure-function relationship of this class. These studies demonstrate the importance of chain length and olefin stereochemistry on inhibitory activity. (C) 2017 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2017.02.066
• 作为产物：
  描述：

  methyl α-bromo-α-(3-methyl-2-butenyl)malonate 在 锌 作用下， 以 溶剂黄146 为溶剂， 生成 dimethyl (3-methyl-2-butenyl)propanedioate
  参考文献：
  名称：

  Cyclobutenes作为金（I）催化的1,8-烯炔的环异构化中的可分离中间体

  摘要：

  Abstractmagnified imageThe gold(I)‐catalysed isomerisation of 1,8‐enynes allows the efficient synthesis of functionalised bicyclo[5.2.0]nonenes. Notably, these cyclobutenes derivatives can be isolated as reactive intermediates that could undergo subsequent gold(I)‐catalysed transformations such as isomerisation, fragmentation or ene reaction to furnish more structurally complex products. This study also provides useful information related to the mechanism leading to metathesis‐type derivatives, examples of which were shown to be produced, in the present case, by a gold(I)‐catalysed ring fragmentation of the cyclobutene moiety.

  DOI：

  10.1002/adsc.200900056

文献信息

• Versatile synthesis of bicyclo[4.3.0]nonenes and bicyclo[4.4.0]decenes by a domino Heck-Diels-Alder reaction
  作者：Kiah How Ang、Stefan Bräse、Arno G. Steinig、Frank E. Meyer、Amadeu Llebaria、Katharina Voigt、Armin de Meijere

  DOI：10.1016/0040-4020(96)00639-4

  日期：1996.8

  afterwards in a one-pot process) to give bicyclo[4.3.0]nonene and bicyclo[4.4.0]-decene derivatives in good to excellent yields. Among the examples reported are the first cases of intramolecular Heck reactions with a (bromomethylene)cyclopropane starter or/and a methylenecyclopropane terminator which occur without ring opening of the cyclopropyl group.

  在钯催化下，将各种2-bromo-1,6-和2-bromo-1,7-二烯进行环化，生成邻位的exodimethylcycloalkanes，它们与亲双烯体反应（既可以在环化过程中存在，也可以在随后的一锅法中加入），从而生成双环[4.3.0]壬烯和双环[4.4.0]-癸烯衍生物具有良好的收率和优异的收率。在所报道的实例中是在没有环丙基的开环的情况下发生的与（溴代亚甲基）环丙烷起始剂或/和亚甲基环丙烷终止剂的分子内Heck反应的第一种情况。
• The Synthesis of α-Azidoesters and Geminal Triazides
  作者：Philipp Klahn、Hellmuth Erhardt、Andreas Kotthaus、Stefan F. Kirsch

  DOI：10.1002/anie.201402433

  日期：2014.7.21

  representatives of this novel class of triazide compounds: Despite their high nitrogen content, the geminal triazides are easy to handle, even when preparative‐scale syntheses are performed. (Caution: These procedures still require protective measures!) The triazides are now broadly available for further studies regarding their properties and reactivity. Furthermore, we show how the method can be used to

  描述了三种简单的合成双三叠氮化物的方法：从1）3-氧代羧酸，2）碘代甲基酮或3）末端烯烃开始，可以通过使用IBX在温和的氧化反应条件下构建一系列三叠氮基甲基酮。 -SO 3 K，2-碘氧苯甲酸（IBX）和NaN 3的磺酰化衍生物作为叠氮化物源。这是该新型三叠氮化物化合物代表的首次报道：尽管三叠氮化物的氮含量很高，但即使进行制备规模的合成，它们仍易于处理。（警告：这些程序仍需要采取保护措施！）三叠氮化物现已广泛用于对其性质和反应性进行进一步研究。此外，我们展示了该方法如何可用于提供α-叠氮酸酯，这是氨基酸的潜在组成部分。
• Lithium Chloride-Mediated Stereoselective Synthesis of Cyclopropanecarboxamides from γ,δ-Epoxy Malonates through a Domino Cyclopropanation/Lactonization/Aminolysis Process
  作者：Marcelo V. Marques、Marcus M. Sá

  DOI：10.1021/jo500712t

  日期：2014.5.16

  synthesis of novel multifunctionalized cyclopropanes from γ,δ-epoxy malonates and amines mediated by LiCl under mild conditions was carried out. This domino reaction involves the initial cyclopropanation via intramolecular ring-opening of γ,δ-epoxy malonates through the cooperative catalysis of LiCl (acting as a Lewis acid) and a Brønsted base (a primary or, in selected cases, a secondary amine). The sequential

  在温和的条件下，由LiCl介导的γ，δ-环氧丙二酸酯和胺进行了立体选择性合成新型多功能环丙烷。该多米诺反应涉及通过LiCl（起路易斯酸的作用）和布朗斯台德碱（伯胺，或在某些情况下，仲胺）的协同催化作用，通过γ，δ-环氧丙二酸酯的分子内开环进行的初始环丙烷化。顺序事件包括内酯环的内酯化和氨解，最终以良好的分离产率为环丙烷甲酰胺提供了不同的取代方式。在所有情况下，四元立体异构中心都可以完美组装，并获得一个非对映异构体。该方法具有较高的原子经济性，具有显着的模块化和操作简单性，并容忍各种功能基团。容易获得的起始原料，广泛的范围以及在环境温度下使用可持续溶剂（甲醇或乙醇）的参与使该多米诺骨牌工艺非常有效。在实验观察的基础上提出了反应机理，涉及环亚丙基内酯的制备和反应性，这是多米诺法的可能中间体。
• Free Radical Cyclizations of Trienes with Tris(Trimethylsilyl)Silane
  作者：Nora E. Restrepo-Sánchez、Fernando J. Gómez、Luz M. Jaramillo-Gómez、Tomas Hudlioky

  DOI：10.1080/00397919908086447

  日期：1999.8

  Abstract The intramolecular trapping of a stabilized intermediate allylic radical generated by the addition of tris(trimethylsilyl)silyl (sisyl) radical to a conjugated system was performed. The observed low stereoselectivity suggests thermodynamic rather than kinetic control in this cyclization process.

  摘要 对通过将三（三甲基甲硅烷基）甲硅烷基（甲硅烷基）自由基加成到共轭体系中产生的稳定的中间烯丙基自由基进行了分子内捕获。观察到的低立体选择性表明在该环化过程中是热力学而不是动力学控制。
• Copper-Mediated Radical–Polar Crossover Enables Photocatalytic Oxidative Functionalization of Sterically Bulky Alkenes
  作者：Nicholas L. Reed、Grace A. Lutovsky、Tehshik P. Yoon

  DOI：10.1021/jacs.1c02747

  日期：2021.4.28

  and exceptionally mild photocatalytic oxidative heterofunctionalization reactions between bulky tri- and tetrasubstituted alkenes and a wide variety of nucleophilic partners. Moreover, we demonstrate that the broad scope of this transformation arises from photocatalytic alkene activation and thus complements existing transition-metal-catalyzed methods for oxidative heterofunctionalization. More broadly

  氧化杂官能化反应是将烯烃和杂原子亲核试剂转化为复杂饱和杂环的最有吸引力的方法之一。然而，最先进的过渡金属催化氧化异质官能化方法通常仅限于不受阻碍的烯烃，并且不同的亲核伙伴通常需要完全不同的反应条件。在这里，我们展示了 Cu(II) 介导的自由基-极性交叉允许在庞大的三取代和四取代烯烃与多种亲核伙伴之间进行高效且异常温和的光催化氧化异功能化反应。而且，我们证明了这种转化的广泛范围源于光催化烯烃活化，因此补充了现有的过渡金属催化氧化异功能化方法。更广泛地说，这些结果进一步表明，Cu(II) 盐是光氧化还原应用的理想末端氧化剂，光催化底物活化和 Cu(II) 介导的自由基氧化的结合可以解决催化氧化化学中长期存在的挑战。