4-((trimethylsilyl)oxy)-3(E)-penten-2-one | 25145-05-5

• 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: 4-((trimethylsilyl)oxy)-3(E)-penten-2-one
• 英文别名: 4-(trimethylsilyloxy)-3-penten-2-one；(E)-4-(trimethylsiloxy)-3-penten-2-one；(E)-4-trimethylsiloxypent-3-en-2-one；(E)-4-((trimethylsilyl)oxy)pent-3-en-2-one；trans-Trimethylsiliconacetylacetonat；4-((Trimethylsilyl)oxy)pent-3-en-2-one；(E)-4-trimethylsilyloxypent-3-en-2-one
• CAS: 25145-05-5
• 化学式: C₈H₁₆O₂Si
• 分子量: 172.299
• InChiKey: FBADCSUQBLLAHW-SOFGYWHQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.33
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 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：

  4-((trimethylsilyl)oxy)-3(E)-penten-2-one 以50%的产率得到
  参考文献：
  名称：

  JULLIEN, J.;PECHINE, J. M.;PEREZ, F.;PIADE, J. J., TETRAHEDRON, 1982, 38, N 10, 1413-1416

  摘要：

  DOI：
• 作为产物：
  描述：

  乙酰丙酮 、 三甲基氰硅烷 以100%的产率得到
  参考文献：
  名称：

  GOSTEVSKIJ B. A.; KRUGLAYA O. A.; ALBANOV A. I.; VYAZANKIN N. S., ZH. OBSHCH. XIMII, 1981, 51, HO 4, 817-820

  摘要：

  DOI：

文献信息

• Oxidative C−C Bond-Forming Reaction of Electron-Rich Alkylbenzyl Ether with Trimethylvinyloxysilane
  作者：Bai-Ping Ying、Bridget G. Trogden、Daniel T. Kohlman、Sidney X. Liang、Yao-Chang Xu

  DOI：10.1021/ol036314j

  日期：2004.5.1

  Treatment of an electron-rich benzyl ether with DDQ at ambient temperature followed by addition of a silyl enol ether undergoes a C-C bond-forming reaction to afford 3-alkoxy-3-phenyl-propionyl compound. This is a general reaction and works well with a variety of silyl enol ethers to give carbonyl products in yields ranging from 10 to 85%.

  在室温下用DDQ处理富电子苄基醚，然后加入甲硅烷基烯醇醚进行CC键形成反应，得到3-烷氧基-3-苯基-丙酰基化合物。这是一般反应，可与多种甲硅烷基烯醇醚很好地反应，以10至85％的收率得到羰基产物。
• Flash vacuum thermolysis of β-keto-trimethylsilyl-enol-ethers
  作者：J. Jullien、J.M. Pechine、F. Perez、J.J. Piade

  DOI：10.1016/0040-4020(82)80222-6

  日期：1982.1

  Thermolysis at 800° of a series of β-keto-trimethylsilyl-enol-ethers allows the elimination of a trimethylsilanol molecule through a 1,5 rearrangement. The reaction products are furanic derivatives, which are obtained in often good yields through an allenic intermediate, which has been isolated.

  一系列β-酮-三甲基甲硅烷基-烯醇醚在800°下热解可通过1,5重排消除三甲基甲硅烷醇分子。反应产物是呋喃衍生物，其通常通过已分离的烯丙基中间体以高收率获得。
• Mechanistic Studies of Ce(IV)-Mediated Oxidation of β-Dicarbonyls:  Solvent-Dependent Behavior of Radical Cation Intermediates
  作者：Jingliang Jiao、Yang Zhang、James J. Devery、Luna Xu、Jennifer Deng、Robert A. Flowers

  DOI：10.1021/jo0625406

  日期：2007.7.1

  The Ce(IV)-initiated oxidation of synthetically relevant β-diketones and β-keto silyl enol ethers was explored in three solvents: acetonitrile, methylene chloride, and methanol. The studies presented herein show that the rate of reaction between Ce(IV) and the substrates is dependent upon the polarity of the solvent. Thermochemical studies and analysis are interpreted to be consistent with transition

  在三种溶剂（乙腈，二氯甲烷和甲醇）中研究了Ce（IV）引发的合成相关的β-二酮和β-酮​​甲硅烷基烯醇醚的氧化。本文介绍的研究表明Ce（IV）与底物之间的反应速率取决于溶剂的极性。热化学研究和分析被认为与过渡态稳定一致，因为溶剂主要负责底物的氧化速率。由β-二酮氧化获得的自由基阳离子的动力学研究表明，通过甲醇直接参与中间体的去质子化，可实现自由基阳离子衰变的更有序过渡态。在衍生自β-酮甲硅烷基烯醇醚的自由基阳离子的情况下，实验数据支持涉及中间体单分子衰变的机制。明显地，衍生自β-二酮和β-酮​​甲硅烷基烯醇醚的自由基阳离子在二氯甲烷中令人惊讶地稳定。
• Stereochemical Determination of Tuscolid/Tuscorons and Total Synthesis of Tuscoron D and E: Insights into the Tuscolid/Tuscoron Rearrangement
  作者：Björn Göricke、Michelle Fernandez Bieber、Kathrin E. Mohr、Dirk Menche

  DOI：10.1002/anie.201906166

  日期：2019.9.9

  tuscolid/tuscorons was determined by a combination of high-field NMR studies, molecular modeling, and chemical derivatization and confirmed by a modular total synthesis of tuscorons D and E. Together with the discovery of three novel tuscorons, this study provides detailed insight into the chemically unprecedented tuscolid/tuscoron rearrangement cascade.

  通过结合高场NMR研究，分子建模和化学衍生化，确定了结构独特的黏细菌聚酮化合物tuscolid / tuscorons的立体化学，并通过模块化合成的tuscorons D和E进行了确证。以及发现了三种新型的tuscorons ，这项研究提供了对化学上空前的托斯科利德/ tus草酮重排级联反应的详细见解。
• Cobalt-mediated solid phase synthesis of 3-O-alkynylbenzyl galactosides and their evaluation as galectin inhibitors
  作者：Anders Bergh、Hakon Leffler、Anders Sundin、Ulf J. Nilsson、Nina Kann

  DOI：10.1016/j.tet.2006.06.057

  日期：2006.8

  Methyl beta-D-galactoside was converted to the corresponding 3,4-O-stannylene acetal, which was selectively benzylated with 3-iodobenzyl bromide and coupled to a polymer-bound propargylic ether via a Sonogashira reaction. The polymer-bound carbohydrate substrate was cleaved from the resin with different carbon nucleophiles in a cobalt-mediated Nicholas reaction. The product 3-O-alkynylbenzyl galactosides were screened towards galectin-1, -3, -7, -8N and -9N in a competitive fluorescence polarisation assay. Particularly potent inhibitors were identified against galectin-7 with affinity enhancements up to one order of magnitude due to the 3-O-alkynylbenzyl moiety. (c) 2006 Elsevier Ltd. All rights reserved.