Dimethyl-((Z)-2-trimethylsilanylmethyl-penta-2,4-dienyl)-amine | 132621-59-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: Dimethyl-((Z)-2-trimethylsilanylmethyl-penta-2,4-dienyl)-amine
• 英文别名: (2Z)-N,N-dimethyl-2-(trimethylsilylmethyl)penta-2,4-dien-1-amine
• CAS: 132621-59-1
• 化学式: C₁₁H₂₃NSi
• 分子量: 197.396
• InChiKey: MDLKEILMDGCZJV-FLIBITNWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.0
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  三甲基氯硅烷 、 2-<(Dimethylamino)methyl>-1,4-pentadiene 在 正丁基锂 作用下， 生成 Dimethyl-((Z)-2-methylene-5-trimethylsilanyl-pent-3-enyl)-amine 、 Dimethyl-((E)-2-methylene-5-trimethylsilanyl-pent-3-enyl)-amine 、 Dimethyl-((Z)-2-trimethylsilanylmethyl-penta-2,4-dienyl)-amine 、 Dimethyl-((E)-2-trimethylsilanylmethyl-penta-2,4-dienyl)-amine
  参考文献：
  名称：

  Highly selective trapping of unsymmetrical pentadienyl anions by silicon and tin electrophiles. Marked contrast between kinetic and thermodynamic control of product composition

  摘要：

  The nucleophilic reaction of lithium and potassium salts of five pentadienyl anions bearing sterically and/or coordinatively different groups at their unsymmetrical 2-position toward Me3SiCl and Me3SnBr is described. When the anion of the potassium salt was trapped by Me3SiCl, (Z)-4-substituted-pentadienylsilanes were obtained with high selectivity (87-100%). The lithium salt, however, gave a mixture of (E)- and (Z)-4-substituted-pentadienylsilanes. The coupling reaction proceeds under kinetic control, because the product composition from Si trapping reflected the structure of the parent dienyl anion and the steric interaction between the incoming Me3Si group and the substituent on the anion. In contrast, when the anion was trapped by Me3SnBr under the identical conditions, (Z)-2-substituted-pentadienyltins were formed with 60-96% selectivity. Only relatively small changes in product composition, as a function of the cation or the substituent on the anion, were observed. These results could be explained by thermodynamic controlling factors, including a 1,5-Me3Sn shift, and a redistribution of pentadienyl groups under basic conditions.

  DOI：

  10.1021/jo00006a011

文献信息

• Highly selective trapping of unsymmetrical pentadienyl anions by silicon and tin electrophiles. Marked contrast between kinetic and thermodynamic control of product composition
  作者：Yoshinori Naruta、Yutaka Nishigaichi、Kazuhiro Maruyama

  DOI：10.1021/jo00006a011

  日期：1991.3

  The nucleophilic reaction of lithium and potassium salts of five pentadienyl anions bearing sterically and/or coordinatively different groups at their unsymmetrical 2-position toward Me3SiCl and Me3SnBr is described. When the anion of the potassium salt was trapped by Me3SiCl, (Z)-4-substituted-pentadienylsilanes were obtained with high selectivity (87-100%). The lithium salt, however, gave a mixture of (E)- and (Z)-4-substituted-pentadienylsilanes. The coupling reaction proceeds under kinetic control, because the product composition from Si trapping reflected the structure of the parent dienyl anion and the steric interaction between the incoming Me3Si group and the substituent on the anion. In contrast, when the anion was trapped by Me3SnBr under the identical conditions, (Z)-2-substituted-pentadienyltins were formed with 60-96% selectivity. Only relatively small changes in product composition, as a function of the cation or the substituent on the anion, were observed. These results could be explained by thermodynamic controlling factors, including a 1,5-Me3Sn shift, and a redistribution of pentadienyl groups under basic conditions.