1,3-di-[(1R,2R,3R,5S)-2,6,6-trimethylbicyclo[3.1.1]hept-3-yl]imidazolium perchlorate | 1351530-61-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 1,3-di-[(1R,2R,3R,5S)-2,6,6-trimethylbicyclo[3.1.1]hept-3-yl]imidazolium perchlorate
• CAS: 1351530-61-4
• 化学式: C₂₃H₃₇N₂*ClO₄
• 分子量: 441.011
• InChiKey: IALJASHJBWTQOT-DFXFRSQESA-M

计算性质

• 辛醇/水分配系数(LogP)：
  0.51
• 重原子数：
  30.0
• 可旋转键数：
  2.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  101.05
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  1,3-di-[(1R,2R,3R,5S)-2,6,6-trimethylbicyclo[3.1.1]hept-3-yl]imidazolium perchlorate 、 chloro(1,5-cyclooctadiene)rhodium(I) dimer 在 lithium tert-butanolate 作用下， 以 四氢呋喃 为溶剂， 以81%的产率得到chloro(η4-1,5-cyclooctadiene)(1,3-di-[(1R,2R,3R,5S)-2,6,6-trimethylbicyclo[3.1.1]hept-3-yl]imidazolin-2-ylidene)rhodium(I)
  参考文献：
  名称：

  Synthesis and characterization of chiral mono N-heterocyclic carbene-substituted rhodium complexes and their catalytic properties in hydrosilylation reactions

  摘要：

  Different chiral mono-substituted N-heterocyclic carbene complexes of rhodium were prepared, starting from [Rh(COD)Cl](2) (COD = cyclooctadiene) by addition of free N-heterocyclic carbenes (NHC), or an in-situ deprotonation of the corresponding iminium salt. All new complexes were characterized by spectroscopy methods. In addition, the structures of chloro(eta(4)-1,5-cyclooctadiene)(1,3-di-[(1R,2R,3R,5S)-2,6,6- trimethylbicyclo[3.1.1]hept-3-yl] imidazolin-2-ylidene) rhodium(I) (5a), chloro(eta(4)-1,5-cyclooctadiene)(1,3-di-[(1R,2S,5R)-2-isopropyl-5-menthylcyclohex-1-yl] imidazol-2-ylidene)rhodium(I) (5b) and chloro(eta(4)-1,5-cyclooctadiene)(1,3-di-[(2R,4S,5S)-2-methyl-4-phenyl-1,3-dioxacyclohex-5-yl]imidazolin-2- ylidene)rhodium(I) (5i) were analyzed by DFT-calculations. The enantioselective hydrosilylation of acetophenone, ethylpyruvate and n-propylpyruvate with diphenylsilane and hydrolysis was carried out with chiral C-2-symmetrical mono-substituted N-heterocyclic carbene rhodium complexes giving for the first time an enantioselective excess of up to 74% ee in the case of the n-propylpyruvate. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2011.04.001
• 作为产物：
  描述：

  草酸醛 、 (1R,2R,3R,5S)-(-)-Isopinocampheylamine 在 高氯酸 作用下， 生成 1,3-di-[(1R,2R,3R,5S)-2,6,6-trimethylbicyclo[3.1.1]hept-3-yl]imidazolium perchlorate
  参考文献：
  名称：

  Synthesis and characterization of chiral mono N-heterocyclic carbene-substituted rhodium complexes and their catalytic properties in hydrosilylation reactions

  摘要：

  Different chiral mono-substituted N-heterocyclic carbene complexes of rhodium were prepared, starting from [Rh(COD)Cl](2) (COD = cyclooctadiene) by addition of free N-heterocyclic carbenes (NHC), or an in-situ deprotonation of the corresponding iminium salt. All new complexes were characterized by spectroscopy methods. In addition, the structures of chloro(eta(4)-1,5-cyclooctadiene)(1,3-di-[(1R,2R,3R,5S)-2,6,6- trimethylbicyclo[3.1.1]hept-3-yl] imidazolin-2-ylidene) rhodium(I) (5a), chloro(eta(4)-1,5-cyclooctadiene)(1,3-di-[(1R,2S,5R)-2-isopropyl-5-menthylcyclohex-1-yl] imidazol-2-ylidene)rhodium(I) (5b) and chloro(eta(4)-1,5-cyclooctadiene)(1,3-di-[(2R,4S,5S)-2-methyl-4-phenyl-1,3-dioxacyclohex-5-yl]imidazolin-2- ylidene)rhodium(I) (5i) were analyzed by DFT-calculations. The enantioselective hydrosilylation of acetophenone, ethylpyruvate and n-propylpyruvate with diphenylsilane and hydrolysis was carried out with chiral C-2-symmetrical mono-substituted N-heterocyclic carbene rhodium complexes giving for the first time an enantioselective excess of up to 74% ee in the case of the n-propylpyruvate. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2011.04.001