sodium hydroxymethylvinylsilanolate | 50977-70-3

• 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: sodium hydroxymethylvinylsilanolate
• CAS: 50977-70-3
• 化学式: C₃H₇O₂Si*Na
• 分子量: 126.163
• InChiKey: VRUHLADYQBWEAZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -3.86
• 重原子数：
  7.0
• 可旋转键数：
  1.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  43.29
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  甲基乙烯基二乙氧基硅烷 在 水 、 sodium hydroxide 作用下， 以15 mg的产率得到sodium hydroxymethylvinylsilanolate
  参考文献：
  名称：

  Mechanistic Studies on the Pd-Catalyzed Vinylation of Aryl Halides with Vinylalkoxysilanes in Water: The Effect of the Solvent and NaOH Promoter

  摘要：

  The mechanism of the Pd-catalyzed vinylation of aryl halides with vinylalkoxysilanes in water has been studied using different catalytic precursors. The NaOH promoter converts the initial vinylalkoxysilane into a highly reactive water-soluble vinylsilanolate species. Similarly, deuterium-labeling experiments have shown that, irrespective of the catalytic precursor used, vinylation occurs exclusively at the CH vinylic functionality via a Heck reaction and not at the C-Si bond via a Hiyama cross-coupling. The involvement of a Heck mechanism is interpreted in terms of the reduced nucleophilicity of the base in water, which disfavors the transmetalation step. The Heck product (beta-silylvinylarene) undergoes partial desilylation, with formation of a vinylarene, by three different routes: (a) hydrolytic desilylation by the aqueous solvent (only at high temperature); (b) transmetalation of the silyl olefin on the PdH Heck intermediate followed by reductive elimination of vinylarene; (c) reinsertion of the silyl olefin into the PdH bond of the Heck intermediate followed by beta-Si syn-elimination. Both the Hiyama and Heck catalytic cycles and desilylation mechanisms b and c have been computationally evaluated for the [Pd(en)Cl-2] precursor in water as solvent. The calculated Gibbs energy barriers support the reinsertion route proposed on the basis of the experimental results.

  DOI：

  10.1021/ja404255u