2-trimethylsilyl-3-buten-2-ol | 75697-67-5

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: 2-trimethylsilyl-3-buten-2-ol
• 英文别名: 2-trimethylsilylbut-3-en-2-ol
• CAS: 75697-67-5
• 化学式: C₇H₁₆OSi
• 分子量: 144.289
• InChiKey: NIYBHDMFRLWOOF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  9.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  2-trimethylsilyl-3-buten-2-ol 、 乙酰氯 在 乙烯基溴化镁 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成 2-Trimethylsilylbut-3-en-2-yl acetate
  参考文献：
  名称：

  Thermal [3,3]-rearrangement of 1,1-disubstituted allyl carboxylates: lone pair participation and the geminal bond participation

  摘要：

  The diastereoselectivity of the [3,3]-rearrangement of 1,1-disubsstituted ally! carboxylates was studied. In this heteroatom-containing system, the transition state has a boat-like transition structure (TS) because of the participation of the lone pairs and the secondary orbital interaction. Although the TS for the [1,3]-rearrangement has a far higher barrier, it does not proceed in the usual antarafacial manner due to the cyclic orbital interaction among two lone pairs of the carboxylate and the allylic lumo. In conjunction with the geminal bond participation, delocalization to the sigma-bond at the Z-position shows a bonding character in the transition state of the [3,3]-rearrangement. Therefore, we predicted that a more electron-withdrawing sigma-bond prefers the Z-position in the product. We designed the 1,1-disubstituted substrates with trimethylsilyl and pentyl groups, and found that the trimethylsilyl group prefers the Z-position despite its steric bulkiness. We confirmed our prediction by experimentation. This Z-selectivity was improved when a trimethylgermyl group was used. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.06.016
• 作为产物：
  描述：

  Lithium; 2-trimethylsilanyl-but-3-en-2-olate 在 水 作用下， 生成 2-trimethylsilyl-3-buten-2-ol
  参考文献：
  名称：

  A general preparative method for .alpha.-lithioethers and its application to a concise, practical synthesis of brevicomin

  摘要：

  DOI：

  10.1021/ja00542a064

文献信息

• “<i>Syn-Effect</i>” in the Desilylation Reaction of γ-Silylated Allylic and Vinylic Sulfones
  作者：Samar Kumar Guha、Yutaka Ukaji、Katsuhiko Inomata

  DOI：10.1246/cl.2003.1158

  日期：2003.12

  The desilylation reaction of γ-silylated allylic sulfones was found to proceed through γ-silylated (E)-vinylic sulfones to afford the corresponding allylic sulfones by treatment with DBU and H2O. The Z/E ratio of the resulting allylic sulfones varied according to the γ-substituents of the γ-silylated sulfones. This stereochemical outcome was rationalized by “syn-effect.”

  研究发现，γ-硅烷化的烯丙基砜通过γ-硅烷化的（E）-乙烯基砜的脱硅反应，在DBU和H2O处理下得到相应的烯丙基砜。所得烯丙基砜的Z/E比率会根据γ-硅烷化砜的γ-取代基的不同而变化。这一立体化学结果可以通过“顺效应”来解释。
• COHEN T.; MATZ J. R., J. AMER. CHEM. SOC., 1980, 102, NO 22, 6900-6902
  作者：COHEN T.、 MATZ J. R.

  DOI：——

  日期：——