| 147438-28-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯内酰胺
• CAS: 147438-28-6；147513-27-7
• 化学式: C₅₂H₈₃NO₁₄
• 分子量: 946.229
• InChiKey: YTAQRMPDCMNLAM-MCQUVAHMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.79
• 重原子数：
  67.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  215.66
• 氢给体数：
  4.0
• 氢受体数：
  14.0

反应信息

• 作为反应物：
  描述：

  在 zinc(II) chloride 作用下， 以 甲醇 为溶剂， 生成
  参考文献：
  名称：

  Studies on the chemistry of rapamycin: Novel transformations under Lewis-acid catalysis

  摘要：

  The reactivity of rapamycin under mild Lewis-acid catalysis has been investigated. The molecule has been found to be extremely sensitive to basic reagents due to carboxylate elimination beta to the C24 ketone. However, transformations normally effected under basic conditions, such as C-13-C-14 benzilic acid rearrangement Of C28-C30 retroaldol, can be achieved on rapamycin itself by catalysis with ZnCl2 in the appropriate solvent. These are novel transformations that circumvent the protection or masking of reactive functional groups and allow efficient degradation of the molecule for synthetic and biological studies.

  DOI：

  10.1016/s0040-4039(00)77473-9
• 作为产物：
  描述：

  甲醇 、 雷帕霉素 在 zinc(II) chloride 作用下， 反应 4.0h， 以78%的产率得到
  参考文献：
  名称：

  Studies on the chemistry of rapamycin: Novel transformations under Lewis-acid catalysis

  摘要：

  The reactivity of rapamycin under mild Lewis-acid catalysis has been investigated. The molecule has been found to be extremely sensitive to basic reagents due to carboxylate elimination beta to the C24 ketone. However, transformations normally effected under basic conditions, such as C-13-C-14 benzilic acid rearrangement Of C28-C30 retroaldol, can be achieved on rapamycin itself by catalysis with ZnCl2 in the appropriate solvent. These are novel transformations that circumvent the protection or masking of reactive functional groups and allow efficient degradation of the molecule for synthetic and biological studies.

  DOI：

  10.1016/s0040-4039(00)77473-9

文献信息

• Studies on selective reductions of rapamycin
  作者：Juan I. Luengo、Leonard W. Rozamus、Dennis A. Holt

  DOI：10.1016/s0040-4039(00)78248-7

  日期：1994.8

  The reaction of rapamycin (1) with different reductive agents has been studied. As expected, the C-14 ketone of the ''tricarbonyl'' unit is the most electrophilic center in the molecule and could be selectively converted to either the alcohol (Zn/AcOH or DIBAL) or to the C-14 methylene (H2S, pyridine/MeOH). Under Luche's conditions, the C-14 carbonyl was protected and reduction took place stereoselectively at both C-24 and C-30 (NaBH4/CeCl3) or exclusively at C-30 (NaBH3CN/CeCl3). Selective reaction at C-30 also took place under Evans conditions with NaBH(OAc)(3). These reactions allow the selective manipulation of the rapamycin ''effector domain''.