(O->Si)chelate N'-(dimethylfluorosilylmethyl)-N'-methyl-N-nosyl-(R,S)-prolinamide | 1384200-34-3

• 英文名称: (O->Si)chelate N'-(dimethylfluorosilylmethyl)-N'-methyl-N-nosyl-(R,S)-prolinamide
• 英文别名: N'-(dimethylfluorosilylmethyl)-N'-methyl-N-(4-nitrobenzenesulfonyl)prolinamide
• CAS: 1384200-34-3
• 化学式: C₁₅H₂₂FN₃O₅SSi
• 分子量: 403.507
• InChiKey: XLWBQOFSKNEDCM-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

• 作为反应物：
  描述：

  三氟甲磺酸三甲基硅酯 、 (O->Si)chelate N'-(dimethylfluorosilylmethyl)-N'-methyl-N-nosyl-(R,S)-prolinamide 以 苯 为溶剂， 反应 3.0h， 以89%的产率得到N'-(dimethyltriflatosilylmethyl)-N-'methyl-N-(4-nitrobenzenesulfonyl)prolinamide
  参考文献：
  名称：

  具有氨基酸部分的单-C,O-螯合溴和三氟甲硅烷：盐或共价键复合物？

  摘要：

  肌氨酸和脯氨酸的衍生物——三氟甲磺酸酯 TsN(Me)CH2C(O)N(Me)-CH2SiMe2OTf 和 Ns-Pro-N(Me)CH2SiMe2OTf（Ns 是 4-NO2C6H4SO2）——是通过三甲基甲硅烷基三氟甲磺酸酯的反应合成的与先前制备的卤代硅烷。溴化物 NsNHCH(Me)C(O)N(Me)CH2SiMe2Br 是通过适当的二硅氧烷的 Si-O-Si 部分与过量乙酰溴的裂解合成的。这些化合物和先前表征的溴化物 TsN(Ac)CH2C(O)N(Me) CH2SiMe2Br 的 X 射线衍射研究表明，三氟甲磺酸酯中的 Si-O 配位键长度为 1.7692(14)– 1.8623(14)一种。溴和硅原子之间的原子间距离为 2.7095(8) 和 2.9704(7) Å，这表明这些键很弱。为了阐明 Si…X 键合 (X = OTf, Br) 的性质，进行了电子密度的拓扑分析并计算了

  DOI：

  10.1007/s11172-019-2429-z
• 作为产物：
  描述：

  1,1,3,3-tetramethyl-1,3-bis[N-methyl-N'-(4-nitrophenylsulfonyl)propylamidomethyl]-1,3-disiloxane 在 三氟化硼乙醚 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以90%的产率得到(O->Si)chelate N'-(dimethylfluorosilylmethyl)-N'-methyl-N-nosyl-(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