28-secorapamycin | 147438-29-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 28-secorapamycin
• 英文别名: [(E,2R,3S,6R)-1-[(1S,3R,4R)-4-hydroxy-3-methoxycyclohexyl]-2,6,8-trimethyl-5,9-dioxonon-7-en-3-yl] (2S)-1-[2-[(2R,3R,6S)-6-[(2S,3E,5E,7E,9S,11R)-2,13-dimethoxy-3,9,11-trimethyl-12-oxotrideca-3,5,7-trienyl]-2-hydroxy-3-methyloxan-2-yl]-2-oxoacetyl]piperidine-2-carboxylate
• CAS: 147438-29-7
• 化学式: C₅₁H₇₉NO₁₃
• 分子量: 914.187
• InChiKey: JTTOTBPBQLZKCX-POKGNQRYSA-N

物化性质

• 沸点：
  932.4±75.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  65
• 可旋转键数：
  26
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  192
• 氢给体数：
  2
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  28-secorapamycin 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 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：

  雷帕霉素 在 zinc(II) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 以70%的产率得到28-secorapamycin
  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

• Selective Epimerization of Rapamycin via a Retroaldol/Aldol Mechanism Mediated by Titanium Tetraisopropoxide
  作者：Wu Yang、Cheryl A. Digits、Marcos Hatada、Surinder Narula、Leonard W. Rozamus、Cameran M. Huestis、Jason Wong、David Dalgarno、Dennis A. Holt

  DOI：10.1021/ol991209o

  日期：1999.12.1

  [GRAPHICS]We describe the efficient and selective epimerization of the immunosuppressant rapamycin to 28-epirapamycin under mild conditions, The mechanism of epimerization involves an equilibrium of the four C28/C29 diastereomers through a two-step retroaldol/aldol (macrocycle ring-opening/ring-closing) sequence. This retroaldol/aldol equilibration is not restricted to rapamycin but is also applicable to acyclic beta-hydroxyketones, A potentially useful extension of this method-the use of beta-hydroxyketones as enolate synthons for effecting inter- or intramolecular aldol reactions under neutral conditions-is demonstrated.