2-(2-triethylsilanyl-6-triethylsilanylmethylphenyl)pyridine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 2-(2-triethylsilanyl-6-triethylsilanylmethylphenyl)pyridine
• 英文别名: 2-(2-triethylsilyl-6-triethylsilylmethylphenyl)pyridine；Triethyl-[2-pyridin-2-yl-3-(triethylsilylmethyl)phenyl]silane；triethyl-[2-pyridin-2-yl-3-(triethylsilylmethyl)phenyl]silane
• 化学式: C₂₄H₃₉NSi₂
• 分子量: 397.751
• InChiKey: RHZOKVUTFFKCKR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.05
• 重原子数：
  27
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(2-triethylsilanyl-6-triethylsilanylmethylphenyl)pyridine 在 四(三苯基膦)钯 、 一氯化碘 、 potassium carbonate 、 caesium carbonate 、 cesium fluoride 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 20.0~100.0 ℃ 、101.33 kPa 条件下， 反应 37.5h， 生成 methyl 2-{1-phenyl-2-(pyridin-2-yl)phenyl}acetate
  参考文献：
  名称：

  Sequential Protocol for C(sp³)–H Carboxylation with CO₂: Transition-Metal-Catalyzed Benzylic C–H Silylation and Fluoride-Mediated Carboxylation

  摘要：

  One of the most challenging transformations in current organic chemistry is the catalytic carboxylation of a C(sp(3))-H bond using CO2 gas, an inexpensive and ubiquitous Cl source. A sequential protocol for C(sp(3))-H carboxylation by employing a nitrogen-directed, metal-assisted, C-H activation/catalytic silylation reaction in conjunction with fluoride-mediated carboxylation with CO2 was established. The carboxylation proceeded only at the benzylic C(sp(3))-Si bond, not at the aromatic C(sp(2))-Si, which is advantageous for further manipulations of the products.

  DOI：

  10.1021/ol301431d
• 作为产物：
  描述：

  2-溴吡啶 在 十二羰基三钌 、 norbornene 作用下， 以 甲苯 为溶剂， 反应 20.0h， 生成 2-(2-triethylsilanyl-6-triethylsilanylmethylphenyl)pyridine
  参考文献：
  名称：

  Sequential Protocol for C(sp³)–H Carboxylation with CO₂: Transition-Metal-Catalyzed Benzylic C–H Silylation and Fluoride-Mediated Carboxylation

  摘要：

  One of the most challenging transformations in current organic chemistry is the catalytic carboxylation of a C(sp(3))-H bond using CO2 gas, an inexpensive and ubiquitous Cl source. A sequential protocol for C(sp(3))-H carboxylation by employing a nitrogen-directed, metal-assisted, C-H activation/catalytic silylation reaction in conjunction with fluoride-mediated carboxylation with CO2 was established. The carboxylation proceeded only at the benzylic C(sp(3))-Si bond, not at the aromatic C(sp(2))-Si, which is advantageous for further manipulations of the products.

  DOI：

  10.1021/ol301431d

文献信息

• Ru₃(CO)₁₂-Catalyzed Silylation of Benzylic C−H Bonds in Arylpyridines and Arylpyrazoles with Hydrosilanes via C−H Bond Cleavage
  作者：Fumitoshi Kakiuchi、Kazuyuki Tsuchiya、Mitsutaka Matsumoto、Eiichiro Mizushima、Naoto Chatani

  DOI：10.1021/ja047040d

  日期：2004.10.1

  Ruthenium-catalyzed silylation of sp3 C-H bonds at a benzylic position with hydrosilanes gave benzylsilanes. For this silylation reaction, Ru3(CO)12 complex showed high catalytic activity. This silylation proceeded at the methyl C-H bond selectively. For this silylation reaction, pyridyl and pyrazolyl groups, and the imino group in hydrazones, can function as a directing group. Several hydrosilanes

  钌催化在苄基位置的 sp3 CH 键与氢硅烷的硅烷化得到苄基硅烷。对于这种硅烷化反应，Ru3(CO)12 配合物表现出很高的催化活性。这种甲硅烷基化选择性地在甲基 CH 键上进行。对于该甲硅烷基化反应，吡啶基和吡唑基以及腙中的亚氨基可作为导向基团。包括三乙基-、二甲基苯基-、叔丁基二甲基-和三苯基硅烷在内的几种氢硅烷可用作甲硅烷基化试剂。sp2 氮原子与钌配合物的配位对于实现这种硅烷化反应很重要。
• Sequential Protocol for C(sp³)–H Carboxylation with CO₂: Transition-Metal-Catalyzed Benzylic C–H Silylation and Fluoride-Mediated Carboxylation
  作者：Tsuyoshi Mita、Kenichi Michigami、Yoshihiro Sato

  DOI：10.1021/ol301431d

  日期：2012.7.6

  One of the most challenging transformations in current organic chemistry is the catalytic carboxylation of a C(sp(3))-H bond using CO2 gas, an inexpensive and ubiquitous Cl source. A sequential protocol for C(sp(3))-H carboxylation by employing a nitrogen-directed, metal-assisted, C-H activation/catalytic silylation reaction in conjunction with fluoride-mediated carboxylation with CO2 was established. The carboxylation proceeded only at the benzylic C(sp(3))-Si bond, not at the aromatic C(sp(2))-Si, which is advantageous for further manipulations of the products.