3-dimethylphenylsilyl-3-buten-2-one

• 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: 3-dimethylphenylsilyl-3-buten-2-one
• 英文别名: 3-(dimethyl(phenyl)silyl)but-3-en-2-one；3-[Dimethyl(phenyl)silyl]but-3-en-2-one
• 化学式: C₁₂H₁₆OSi
• 分子量: 204.344
• InChiKey: HZVRNNHJYDUVFU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.29
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (E/Z)-dimethyl(1-methyl-1-propenyl)phenylsilane 在 吡啶 、 4-二甲氨基吡啶 、 5E-4 M TPP 、 氧气 、 乙酸酐 作用下， 以 乙酸甲酯 为溶剂， 反应 8.0h， 以48%的产率得到3-dimethylphenylsilyl-3-buten-2-one
  参考文献：
  名称：

  One-Pot Synthesis of α-Trimethylsilyl Enones from Vinylsilanes

  摘要：

  在乙酸酐和吡啶的存在下，通过乙烯基硅烷的光氧化反应可以中等至良好的产率获得α-三甲基硅基烯酮1。由于所需的起始材料易于获得，因此本方法为现有制备α-三甲基硅基烯酮1的方法提供了一个有用的替代方案。

  DOI：

  10.1055/s-1994-25433

文献信息

• Ru-Catalyzed Migratory Geminal Semihydrogenation of Internal Alkynes to Terminal Olefins
  作者：Lijuan Song、Qiang Feng、Yong Wang、Shengtao Ding、Yun-Dong Wu、Xinhao Zhang、Lung Wa Chung、Jianwei Sun

  DOI：10.1021/jacs.9b09658

  日期：2019.10.30

  the gem-H2 Ru-carbene might be the key intermediate in both gem- and trans-addition reactions, rather than the Ru-vinylidene intermediate. The DFT results were further supported by carefully designed control experiments. This uncommon gem-addition combined with 1,2-silyl migration in the metal-carbene intermediate should open up a new synthetic avenue for alkyne transformations.

  炔烃半氢化为烯烃代表了一种基本有用的转化。除了众所周知的顺式和反式半氢化之外，本文还描述了以 1,2-迁移为特征的内部炔烃的孪生半氢化，这为获得有用的末端乙烯基硅烷提供了新的途径。该过程还提供了一种新的甲硅烷基炔烃反应模式。通过正确选择阳离子 [CpRu(MeCN)3]PF6 催化剂和合适的甲硅烷基，芳基和烷基取代的甲硅烷基炔烃都可以参与这种高效的宝石选择性过程。此外，专用条件优化还允许通过使用参数组合（包括合适的甲硅烷基、添加剂和 H2 压力）将选择性从 gem 切换到 trans。对反应机理的系统 DFT 研究表明，gem-H2 Ru-卡宾的形成可能是 gem-和反式加成反应的关键中间体，而不是 Ru-亚乙烯基中间体。精心设计的对照实验进一步支持了 DFT 结果。这种罕见的宝石加成与金属-卡宾中间体中的 1,2-甲硅烷基迁移相结合，应该为炔烃转化开辟了一条新的合成途径。
• Highly Regio- and Diastereoselective One-Pot Synthesis of Silyl Epoxy Alcohols and Vinylsilanes by Direct Hydroxy-Epoxidation
  作者：Waldemar Adam、Markus J. Richter

  DOI：10.1021/jo00091a021

  日期：1994.6

  A direct synthesis of silyl epoxy alcohols from vinyl silanes is described. It consists of the regioselective ene reaction of the vinylsilanes with singlet oxygen, which proceeds with predominant hydrogen abstraction at the position geminal to the silyl group. The resulting silyl allylic hydroperoxides were treated, without isolation, subsequently with Ti(O-i-Pr)(4) to afford the silyl epoxy alcohols in good yields and very high diastereomeric ratios, which ranged from 93:7 to greater than 97:3. Alternatively, the vinylsilanes were photooxygenated directly in the presence of the titanium catalyst and the silyl epoxy alcohols obtained in good yields. The method was applied to di- and trisubstituted acyclic vinylsilanes with a methyl group geminal to silicon and cyclic derivatives all give consistently good results. In this novel hydroxy-epoxidation, the regioselectivity of the singlet oxygen ene reaction as well as the diastereoselectivity of the oxygen transfer can be controlled by the steering effects of the silyl group.
• Epoxidation versus Allylic Oxidation (CH Insertion) in the Oxyfunctionalization of Vinylsilanes and β-Hydroxy Derivatives by Dimethyldioxirane
  作者：W Adam

  DOI：10.1016/00404-0399(50)0960k-

  日期：1995.7.10
• One-Pot Synthesis of α-Trimethylsilyl Enones from Vinylsilanes
  作者：Waldemar Adam、Markus J. Richter

  DOI：10.1055/s-1994-25433

  日期：——

  Photooxygenation of vinylsilanes in the presence of acetic anhydride and pyridine afforded α-trimethylsilyl enones 1 in moderate to good yields. Since the required starting materials are readily available, the present approach constitutes a useful alternative to existing methods for the preparation of α-trimethylsilyl enones 1.

  在乙酸酐和吡啶的存在下，通过乙烯基硅烷的光氧化反应可以中等至良好的产率获得α-三甲基硅基烯酮1。由于所需的起始材料易于获得，因此本方法为现有制备α-三甲基硅基烯酮1的方法提供了一个有用的替代方案。