(Z)-((1-ethoxy-2-phenylvinyl)oxy)trimethylsilane | 78935-61-2

• 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: (Z)-((1-ethoxy-2-phenylvinyl)oxy)trimethylsilane
• 英文别名: [(Z)-1-ethoxy-2-phenylethenoxy]-trimethylsilane
• CAS: 78935-61-2
• 化学式: C₁₃H₂₀O₂Si
• 分子量: 236.386
• InChiKey: YXPSDXJGPQXTJG-QBFSEMIESA-N

物化性质

• 沸点：
  271.5±33.0 °C(Predicted)
• 密度：
  0.966±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.87
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (Z)-((1-ethoxy-2-phenylvinyl)oxy)trimethylsilane 在 三氟甲基次氟酸酯 作用下， 以 various solvent(s) 为溶剂， 反应 3.0h， 生成 fluoro-phenyl-acetic acid ethyl ester
  参考文献：
  名称：

  .alpha.-Fluorination of carbonyl compounds with trifluoromethyl hypofluorite

  摘要：

  DOI：

  10.1021/ja00534a053
• 作为产物：
  描述：

  苯乙酸乙酯 生成 (Z)-((1-ethoxy-2-phenylvinyl)oxy)trimethylsilane
  参考文献：
  名称：

  由乙烯酮甲硅烷基缩醛和N-（烷基氨基）苯并三唑制备β-氨基酯

  摘要：

  通过衍生自乙烯酮甲硅烷基乙缩醛的锂酯烯醇化物与N-（烷基氨基）苯并三唑反应，可以以高收率制得各种各样的β-氨基酯。在去质子化时，仲β-氨基酯容易环化为β-内酰胺（2-氮杂环丁烷酮）。

  DOI：

  10.1016/s0040-4039(00)94482-4

文献信息

• Synthetic Strategies for the Synthesis and Transformation of Substituted Pyrrolinones as Advanced Intermediates for Rhazinilam Analogues
  作者：Inga Kholod、Olivier Vallat、Ana-Maria Buciumas、Antonia Neels、Reinhard Neier

  DOI：10.1002/ejoc.201402903

  日期：2014.12

  The biaryl core structure of rhazinilam with its fixed dihedral angle is a pivotal element for its unique in vitro cytotoxic activity. Most of the related natural products are oxidized versions of rhazinilam. Replacing the sensitive pyrrole ring by a pyrrolinone ring is the basis of our initial strategy towards rhazinilam analogues. With this goal, variants of the sequence crossed Mukaiyama aldol reaction

  具有固定二面角的 rhazinilam 的联芳核心结构是其独特的体外细胞毒活性的关键因素。大多数相关的天然产物是氧化形式的 rhazinilam。用吡咯啉酮环代替敏感的吡咯环是我们对罗嗪类似物的初步策略的基础。为了这个目标，研究了与向山羟醛反应和施陶丁格反应交叉的序列变体。将适当取代的苯乙酮与 O-甲基 O-三甲基甲硅烷基乙烯酮缩醛反应以良好至极好的产率得到吡咯啉酮 8a 和 8b。这些中间体可以通过四个高产率步骤转化为吡咯前体 7a-c，其中包含构建 rhazinilam 环 A、B 和 C 所需的所有原子。我们的研究表明这些中间体缺乏稳定性。描述了针对该中心联芳基核结构的替代合成方法。
• Organosilicon Reducing Reagents for Stereoselective Formations of Silyl Enol Ethers from α-Halo Carbonyl Compounds
  作者：Suman Pramanik、Supriya Rej、Shun Kando、Hayato Tsurugi、Kazushi Mashima

  DOI：10.1021/acs.joc.7b03005

  日期：2018.2.16

  byproducts. Due to the inertness of the reaction byproducts, we found a one-pot transformation of the in situ generated silyl enol ethers into various α-functionalized carbonyls by reaction with Togni-II reagent or aldehydes.

  通过用2,3,5,6-四甲基-1,4-双（三甲基甲硅烷基）-1,4-二氢吡嗪处理α-卤代羰基化合物来实现甲硅烷基烯醇醚的无盐立体选择性合成。在该反应中，产生易除去的三甲基甲硅烷基卤化物和2,3,5,6-四甲基吡嗪作为反应副产物。由于反应副产物的惰性，我们发现通过与Togni-II试剂或醛反应，将原位生成的甲硅烷基烯醇醚一锅转化为各种α-官能化羰基。
• α-Allylation of Carbonyl Compounds via Silyl Enol Ethers and Silyl Ketene Acetals using a Hypervalent Iodine Reagent†
  作者：Robert M. Moriarty、Widanagamage R. Epa、Om Prakash

  DOI：10.1039/a701224a

  日期：——

  allyltrimethylsilane with iodosobenzene and trimethylsilyl trifluoromethanesulfonate followed by treatment with trimethylsilyl enol ethers of ketones or trimethylsilyl ketene acetals of esters/lactones provides a new method for the α-allylation of the corresponding carbonyl compounds.

  烯丙基三甲基硅烷用碘代苯和三氟甲磺酸三甲基甲硅烷基酯氧化，然后用酮的三甲基甲硅烷基烯醇醚或酯/内酯的三甲基甲硅烷基烯酮缩醛处理，为相应羰基化合物的 α-烯丙基化提供了一种新方法。
• Selective, Electrophilic Fluorinations Using N-Fluoro-o-benzenedisulfonimide
  作者：Franklin A. Davis、Wei Han、Christopher K. Murphy

  DOI：10.1021/jo00120a014

  日期：1995.7

  The synthesis of N-fluoro-o-benzenedisulfonimide (NFOBS, 2) and its use as an ''electrophilic'' fluorinating reagent with nucleophilic substrates is described and compared with that of N-fluorobenzenesulfonimide (NFSi, 3). NFOBS (2) is prepared in three steps in 81% overall yield from commercially available o-benzenedisulfonic acid (4) and involves treatment of o-benzenedisulfonimide (6) with dilute fluorine (10% F-2/N-2). Reaction of 2 with metal enolates, silyl enol ethers, and 1,3-dicarbonyl compounds affords the corresponding alpha-fluoro compounds in yields up to 95%, with good control of mono- and difluorination. Fluorination of ortho-metalated aromatic compounds was achieved in modest to good yields (10-80%). While the reactivities of 2 and 3 are similar, better yields were observed with the former reagent in the fluorination of metal enolates, Grignard and lithium reagents, while 3 gave better results with the ortho-lithiated aromatic substrates. The available evidence suggests an S(N)2-type mechanism for the fluorination of nucleophilic substrates by these reagents.
• Emde, Herbert; Simchen, Gerhard, Liebigs Annalen der Chemie, 1983, # 5, p. 816 - 834
  作者：Emde, Herbert、Simchen, Gerhard

  DOI：——

  日期：——