triethoxy((E)-[1,2-D2]vinyl)silane | 1260183-74-1

• 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: triethoxy((E)-[1,2-D2]vinyl)silane
• 英文别名: (E)-tris(ethoxy)(vinyl-d2)silane；(E)-triethoxy(vinyl-d2)silane
• CAS: 1260183-74-1
• 化学式: C₈H₁₈O₃Si
• 分子量: 192.299
• InChiKey: FWDBOZPQNFPOLF-XFMOQSGESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.76
• 重原子数：
  12.0
• 可旋转键数：
  7.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  27.69
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  4-碘苯甲酸 、 triethoxy((E)-[1,2-D2]vinyl)silane 在 sodium hydroxide 、 [Pd(en)Cl₂] 、 重水 作用下， 反应 24.0h， 以63%的产率得到
  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
• 作为产物：
  描述：

  乙炔-1,2-D2 、 三乙氧基硅烷 在 chloro(1,5-cyclooctadiene)rhodium(I) dimer 作用下， 反应 18.0h， 以52%的产率得到triethoxy((E)-[1,2-D2]vinyl)silane
  参考文献：
  名称：

  乙炔-d 2的硅氢加成反应立体选择性合成（E）-和（Z）-三乙氧基（乙烯基-d 2）硅烷

  摘要：

  用三乙氧基硅烷氘化乙炔的氢化硅烷化可涉及任一的合成顺式或反式三乙氧基（乙烯基- d 2通过金属催化剂的一种合适的选择）硅烷。另外，我们证明了设计氢化硅烷化-芳基化顺序过程的可行性，其中乙炔可以在两个反应中使用相同的Pd催化剂转化为苯乙烯或对苯乙烯。

  DOI：

  10.1021/om101127t

文献信息

• Gordillo, Alvaro; Jesus, Ernesto de; Lopez-Mardomingo, Carmen, Journal of the American Chemical Society, 2009, vol. 131, p. 4584 - 4585
  作者：Gordillo, Alvaro、Jesus, Ernesto de、Lopez-Mardomingo, Carmen

  DOI：——

  日期：——