methyl 3-propionate | 131195-57-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: methyl 3-propionate
• 英文别名: methyl 3-(1,1,1,3,3,3-hexamethyl-2-(trimethylsilyl)trisilan-2-yl)propanoate；Methyl 3-tris(trimethylsilyl)silylpropanoate
• CAS: 131195-57-8
• 化学式: C₁₃H₃₄O₂Si₄
• 分子量: 334.754
• InChiKey: ZYQWKQVBFQKYJL-UHFFFAOYSA-N

物化性质

• 沸点：
  304.2±44.0 °C(Predicted)
• 密度：
  0.859±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.25
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl 3-propionate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 20.0h， 以94%的产率得到3-[tris(trimethylsilyl)silyl]propanol
  参考文献：
  名称：

  Modification and chemical transformation of Si(111) surface

  摘要：

  Modification of hydrogen-terminated Si(111) surfaces by hydrosilylation of activated alkenes and further chemical transformation of the modified surfaces is reported. A Si(111)-H surface was reacted with activated alkenes such as acrylate esters, acrylonitrile, and maleic anhydride under mild conditions to give modified surfaces with terminal functional groups. A modified surface with a terminal ester group was reduced by LiAlH4 to give a hydroxy-terminated surface, and the hydroxy-terminated surface was transformed to a bromo-terminated surface. XPS analysis revealed that the brominated surface ( Si(111)-CH2CH2CH2Br) had 32% coverage with the 3-bromopropyl group. Ester and amide formation reactions were carried out on hydroxy- and carboxy-terminated Si surfaces by reaction with tert-butoxycarbonyl glycine, glycine tort-butyl ester, 2,2,2-trifluoroethanol and 4-trifluoromethylbenzyl alcohol in the presence of carbodiimide. XPS characterization indicated that the esters and amide were successfully formed with coverage ranging from 16% to 58%. Coverage ratios of octadecyl ester modified surfaces were also estimated by combination of surface reduction and gas chromatography analysis to be 25-35%. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.09.048
• 作为产物：
  描述：

  tris(trimethylsilyl)silane 、 丙烯酸甲酯（MA） 在 二叔丁基过氧化物 作用下， 以 苯 为溶剂， 生成 methyl 3-propionate
  参考文献：
  名称：

  三（三甲基甲硅烷基）甲硅烷基与三（三甲基甲硅烷基）甲硅烷基：自由基反应性和氧化能力

  摘要：

  提供了三（三甲基甲硅烷基）甲硅烷基I和三（三甲基甲硅烷基）甲锗烷基II自由基反应性的比较。通过激光闪光光解，量子力学计算和电子自旋共振（ESR）实验检查了它们的形成以及在多种化学过程（双键加成，卤素抽象，过氧自由基形成等）中遇到的反应性。起始化合物（TMS）3 GeH比（TMS）3 SiH对叔丁氧基，叔丁基过氧基和膦酰基具有更高的反应性。对于芳族酮三重态也观察到类似的行为。II表现出较低的绝对电负性：因此，向富电子的烯烃中添加的效率低于I的效率。还发现自由基II对于过氧化（II + O2→II-O2）和卤素提取反应均具有较低的反应性。II-O2的重排比I-O2的重排慢；这与过程各自的放热有关。

  DOI：

  10.1016/j.jorganchem.2008.08.039

文献信息

• Alkyl isocyanides as precursors for the formation of carbon-carbon bonds
  作者：C. Chatgilialoglu、B. Giese、B. Kopping

  DOI：10.1016/s0040-4039(00)98016-x

  日期：1990.1

  Tris(trimethylsilyl)silane is an effective mediator for the formation of carbon-carbon bonds via radicals using alkyl isocyanides as precursors.

  三（三甲基甲硅烷基）硅烷是通过使用烷基异氰化物作为前体的自由基形成碳-碳键的有效介体。
• Twofold Radical-Based Synthesis of <i>N</i>,<i>C</i>-Difunctionalized Bicyclo[1.1.1]pentanes
  作者：Helena D. Pickford、Jeremy Nugent、Benjamin Owen、James. J. Mousseau、Russell C. Smith、Edward A. Anderson

  DOI：10.1021/jacs.1c04180

  日期：2021.7.7

  Bicyclo[1.1.1]pentylamines (BCPAs) are of growing importance to the pharmaceutical industry as sp3-rich bioisosteres of anilines and N-tert-butyl groups. Here we report a facile synthesis of 1,3-disubstituted BCPAs using a twofold radical functionalization strategy. Sulfonamidyl radicals, generated through fragmentation of α-iodoaziridines, undergo initial addition to [1.1.1]propellane to afford iodo-BCPAs;

  双环[1.1.1] pentylamines（BCPAs）是重要性日益增加，以制药业作为藻3个苯胺和富含的bioisosters ñ -叔丁基的基团。在这里，我们报告了使用双重自由基功能化策略轻松合成 1,3-二取代 BCPA。磺胺基自由基，通过 α-碘氮丙啶的碎裂产生，经过初始添加到 [1.1.1] 丙烷中，得到碘-BCPA；然后通过甲硅烷基介导的 Giese 反应将这些产物中新形成的 C-I 键功能化。这种化学反应也可以顺利转化为 1,3-二取代碘-BCP。可容纳多种自由基受体和碘-BCPA，可直接获取一系列有价值的类苯胺等排体。
• Isonitriles as Alkyl Radical Precursors in Visible Light Mediated Hydro‐ and Deuterodeamination Reactions**
  作者：Irene Quirós、María Martín、Miguel Gomez‐Mendoza、María Jesús Cabrera‐Afonso、Marta Liras、Israel Fernández、Luis Nóvoa、Mariola Tortosa

  DOI：10.1002/anie.202317683

  日期：2024.2.12

  We report the use of isonitriles as alkyl radical precursors in visible-light mediated hydro- and deuterodeamination reactions. Most examples only require visible-light irradiation of the isonitrile in the presence of a silyl radical precursor, although a significant acceleration was observed in the presence of an organic photocatalyst. The method is scalable, shows broad functional group compatibility

  我们报道了在可见光介导的加氢和氘代脱氨基反应中使用异腈作为烷基自由基前体。大多数例子仅需要在甲硅烷基自由基前体存在下对异腈进行可见光照射，尽管在有机光催化剂存在下观察到显着的加速。该方法具有可扩展性，显示出广泛的官能团兼容性，并且适用于 C α伯、C α仲和 C α叔烷基异腈。
• Tris(trimethylsilyl)silane: an efficient hydrosilylating agent of alkenes and alkynes
  作者：B. Kopping、C. Chatgilialoglu、M. Zehnder、B. Giese

  DOI：10.1021/jo00040a048

  日期：1992.7

  Tris(trimethylsilyl)silane adds across the double bond of a variety of mono-, di-, and trisubstituted olefins under free-radical conditions in good yields. The reaction, which proceeds via a free-radical chain mechanism, is highly regioselective (anti-Markovnikov). Addition to prochiral olefins bearing an ester group is highly stereoselective. The factors that control the stereochemistry have been discussed terms of preferred conformations of the intermediate carbon-centered radicals and are thought to be of steric origin.
• Tris(trimethylsilyl)silane (TTMSS): formation of carbon-centered radicals from 1,3-dithiolanes and 1,3-dithianes
  作者：Prabhat Arya、Connie Samson、Maurice Lesage、David Griller

  DOI：10.1021/jo00313a008

  日期：1990.12

  Tris(trimethylsilyl)silane (TTMSS), a nontoxic reagent, can be used to generate carbon-centered radicals from 1,3-dithiolanes and 1,3-dithianes.