(O->Si)chelate N'-(dimethylfluorosilylmethyl)-N'-methyl-N-mesyl-(R,S)-prolinamide | 1384200-12-7

• 英文名称: (O->Si)chelate N'-(dimethylfluorosilylmethyl)-N'-methyl-N-mesyl-(R,S)-prolinamide
• CAS: 1384200-12-7
• 化学式: C₁₀H₂₁FN₂O₃SSi
• 分子量: 296.438
• InChiKey: HHHUEAQPXYURFX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  1,3-bis(N'-mesyl-N-methylprolinamidomethyl)-1,1,3,3-tetramethyl-1,3-disiloxane 在 三氟化硼乙醚 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以87%的产率得到(O->Si)chelate N'-(dimethylfluorosilylmethyl)-N'-methyl-N-mesyl-(R,S)-prolinamide
  参考文献：
  名称：

  Synthesis, Structures, and Stereodynamic Behavior of Novel Pentacoordinate Fluorosilanes: Fluorosilyl Derivatives of Proline

  摘要：

  The (O -> Si)-chelate N'-(dimethylfluorosilylmethyl))-N'-methyl-N-(organosulfonyl)prolinamides RSO2-Pro-N(Me)CH2SiMe2F (2a-f, R = Me (a), Ph (b), 4-MeC6H4 (c), 4-ClC6H4 (d), 4-BrC6H4 (e), 4-NO2C6H4 (f)) were synthesized from the corresponding disiloxanes 1a-f using Et2O center dot BF3. According to the NMR and IR data, the extent of dimerization of fluorosilanes 2a-f in solution is negligible, while the O -> Si coordination in solution is weaker than that in the solid state. Comparative CP/MAS NMR and X-ray diffraction studies revealed that in solution the coordination Si-O bond length varies in a narrow range (2.22-2.24 angstrom) that is 0.02-0.11 angstrom longer than in the crystalline state. Dynamic NMR (DNMR) studies of the fluorides revealed a fine structure of the F-19 signals in the 0-20 degrees C temperature range, which was related to the structural features of the coordination set in these complexes. The temperature dependence of the SiMe2 signals in the H-1 DNMR spectra was attributed to a permutational isomerization process involving a positional exchange of equatorial ligands. The narrow range of activational barriers of the process (23-24 kcal mol(-1) and more) and high negative values of the entropy of activation are similar to those observed earlier for Si-substituted N-(dimethylsilylmethyl) and N-(methylphenylsilylmethyl) amides and lactams, which suggests similar permutational processes in all cases. Gas-phase quantum chemical studies demonstrate that the solvation of F- reduces the activation barrier.

  DOI：

  10.1021/om3002697