1-phenyl-3-(trimethylsilyl)-1,2-propadiene | 31650-07-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-phenyl-3-(trimethylsilyl)-1,2-propadiene
• 英文别名: trimethyl(3-phenylpropa-1,2-dien-1-yl)silane；1-Phenyl-3-trimethylsilylallen；1-Trimethylsilyl-3-phenyl-allen；1-trimethylsilyl-3-phenylpropa-1,2-diene
• CAS: 31650-07-4
• 化学式: C₁₂H₁₆Si
• 分子量: 188.345
• InChiKey: HVIIVXLSXPPZMA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.73
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  三甲基-[(E)-2-苯乙烯基]硅烷 在 sodium hydroxide 、 甲基锂 、 十六烷基三甲基溴化铵 作用下， 生成 1-phenyl-3-(trimethylsilyl)-1,2-propadiene
  参考文献：
  名称：

  Stereocontrol in ene-dimerisation and trimerisation of 1-trimethylsilyl-3-phenylcyclopropene

  摘要：

  1-Trimethylsilyl-3-phenylcyclopropene undergoes a highly stereocontrolled ene-reaction to give a dimer and further reaction leads to one or more trimers derived through two ene-reactions. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.12.111

文献信息

• Rh(II)-Catalyzed Alkynylcyclopropanation of Alkenes by Decarbenation of Alkynylcycloheptatrienes
  作者：Mauro Mato、Marc Montesinos-Magraner、Arnau R. Sugranyes、Antonio M. Echavarren

  DOI：10.1021/jacs.1c05422

  日期：2021.7.21

  (including derivatives of complex drug-like molecules), versatile intermediates that previously required much lengthier synthetic approaches. Combining experiments and DFT calculations, the complete mechanistic picture for the divergent reactivity of alkynylcycloheptatrienes under metal catalysis has been unveiled, rationalizing the unique selectivity displayed by rhodium(II) complexes.

  炔基环丙烷在有机合成和药物化学方面都有着广阔的应用前景，但由于其制备过程中存在的挑战，其研究仍相当不足。我们描述了一种基于铑 (II) 催化的 7-炔基环庚三烯脱碳化的烯烃炔基环丙烷化的便捷两步方法。所采用的催化系统规避了与这些底物相关的基本问题，这些底物通常在金属催化下通过6-内环化或环收缩途径演变。这种独特的性能可以快速访问各种炔基环丙烷（包括复杂的类药物分子的衍生物）库，这是以前需要更长的合成方法的多功能中间体。结合实验和DFT计算，揭示了金属催化下炔基环庚三烯不同反应性的完整机理图，合理化了铑(II)配合物所表现出的独特选择性。
• Chemistry of Silylketenes: Simple Preparation of Silylallenes by the Reaction of Silylketenes with Phosphorus Ylides.
  作者：Yasuyuki KITA、Yasunori TSUZUKI、Shinji KITAGAKI、Shuji AKAI

  DOI：10.1248/cpb.42.233

  日期：——

  Reaction of silylketenes 1a, b with stabilized ylides 2a-e readily gave silylallenes 3a-f in high yields. However, similar reaction of 1a with the less stable ylides 2f, g resulted in low yields of the allenes 3 g, h. Use of silylketenes 5a, c with an additional trimethylsilyl group overcame this problem to give silylallenes 3c, g-k directly in considerable to good yields. In this reaction, the additional trimethylsilyl group apparently worked as a masking group.

  甲硅烷基乙烯酮1a、b与稳定的叶立德2a-e的反应容易地以高产率得到甲硅烷基丙二烯3a-f。然而，1a 与稳定性较差的叶立德 2f、g 的类似反应导致丙二烯 3 g、h 的产率较低。使用具有附加三甲基甲硅烷基的甲硅烷基烯酮5a、c克服了该问题，以相当高的收率直接得到甲硅烷基丙二烯3c、g-k。在该反应中，额外的三甲基甲硅烷基显然起到了掩蔽基团的作用。
• Silyation de derives carbonyles α,β-acetyleniques. Synthese d'allenoxysilanes
  作者：G. Merault、P. Bourgeois、J. Dunogues、N. Duffaut

  DOI：10.1016/s0022-328x(00)90310-3

  日期：1974.8

  In the presence of magnesium and in hexamethylphosphoric triamide (HMPT), trimethylchlorosilane reacts with α,β-acetylenic ketones to give in most cases 1,4 addition of two trimethylsilyl groups to the conjugated system: allenoxysilanes, which constitute a new class of organometallic compounds, are formed. These upon hydrolysis give the corresponding silylated α,β-ethylenic ketones. Other reactions

  在镁存在下和六甲基磷三酰胺（HMPT）中，三甲基氯硅烷与α，β-炔酮反应，在大多数情况下使共轭体系中有1,4个两个三甲基甲硅烷基加成：烯丙氧基硅烷，这构成了一类新的有机金属化合物， 形成。这些在水解时得到相应的甲硅烷基化的α，β-烯酮。还发生了其他反应：完全还原羰基，得到多甲硅烷基化的丙二烯；还原复制伴随O-硅烷化和烯醇化。α，β-乙炔醛会发生相同类型的反应。
• Stereo- and regiocontrol in ene-dimerisation and trimerisation of 1-trimethylsilyl-3-phenylcyclopropene
  作者：Andrey E. Sheshenev、Mark S. Baird、Ivan G. Bolesov、Alexandre S. Shashkov

  DOI：10.1016/j.tet.2009.10.077

  日期：2009.12

  1-Trimethylsilyl-3-phenylcyclopropene and its 2D-analog undergo a highly stereocontrolled ene-reaction to give a single dinner. Further reaction leads to one or more trimers derived through two ene-reactions. The dinner formed easily undergoes cycloaddition with active dienes and nitrile oxides while the trimers do not react under the same conditions. The first enantioselective example of an ene-reaction of cyclopropene derivatives using optically active 1-trimethylsilyl-3S-phenylcyclopropene is also discussed. (C) 2009 Elsevier Ltd. All rights reserved.
• Metallation-silylation and kinetic studies of arylmethylacetylenes
  作者：James Y. Becker

  DOI：10.1016/s0022-328x(00)93205-4

  日期：1976.10