(2E,6E)-(4R,8R)-9-((1S,3R,4R)-4-Hydroxy-3-methoxy-cyclohexyl)-2,4,8-trimethyl-5-oxo-nona-2,6-dienal | 146404-45-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2E,6E)-(4R,8R)-9-((1S,3R,4R)-4-Hydroxy-3-methoxy-cyclohexyl)-2,4,8-trimethyl-5-oxo-nona-2,6-dienal
• CAS: 146404-45-7
• 化学式: C₁₉H₃₀O₄
• 分子量: 322.445
• InChiKey: APMKPPLYPNUCCC-WRUAIXNOSA-N

物化性质

• 沸点：
  467.3±45.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  23.0
• 可旋转键数：
  8.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  63.6
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  雷帕霉素 在 氰化四丁基铵 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 1.0h， 生成 (2E,6E)-(4R,8R)-9-((1S,3R,4R)-4-Hydroxy-3-methoxy-cyclohexyl)-2,4,8-trimethyl-5-oxo-nona-2,6-dienal
  参考文献：
  名称：

  从与雷帕霉素和FK506由反应有效地除去2-哌啶的Ñ -Bu 4 Ñ + CN -

  摘要：

  雷帕霉素（反应1）和FK506（11）配有Ñ -Bu 4 Ñ + CN - /水溶液。THF导致其哌考林酯亚基的有效切除，分别导致化合物3和12的良好收率。发生两个连续的环裂解反应：三羰基官能团的快速氰化物促进的断裂，然后是较慢的氰化物催化的酯裂解。氰化物试剂为结构复杂的底物中的分子内酯交换反应提供了温和的化学选择性系统。

  DOI：

  10.1016/s0040-4039(00)60634-2

文献信息

• Base catalyzed degradations of rapamycin
  作者：Robert J. Steffan、Robert M. Kearney、David C. Hu、Amedeo A. Failli、Jerauld S. Skotnicki、Robert A. Schiksnis、James F. Mattes、Kelvin W. Chan、Craig E. Caufield

  DOI：10.1016/s0040-4039(00)79204-5

  日期：1993.6

  The base catalyzed degradation of rapamycin was re-examined and a sequence of steps involving β-elimination, retro-aldol cleavage and benzilic acid rearrangement occur leading to several new products.

  重新检查了雷帕霉素在碱催化下的降解，并进行了一系列涉及β消除，逆向羟醛裂解和苯甲酸重排的步骤，从而产生了几种新产品。
• Degradation of rapamycin: Retrieval of major intact subunits.
  作者：Daniel Yohannes、Samuel J. Danishefsky

  DOI：10.1016/s0040-4039(00)60797-9

  日期：——

  The degradation of rapamycin has made available key substructures which have defined the structures of advanced synthetic intermediates.
• Studies on the chemistry of rapamycin: Novel transformations under Lewis-acid catalysis
  作者：Juan I. Luengo、Arda L. Konialian、Dennis A. Holt

  DOI：10.1016/s0040-4039(00)77473-9

  日期：1993.2

  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.
• Degradation of rapamycin: Synthesis of a rapamycin derived fragment containing the tricarbonyl and triene sectors
  作者：Daniel Yohannes、Cheryl D. Myers、Samuel J. Danishefsky

  DOI：10.1016/s0040-4039(00)60349-0

  日期：1993.3

  A degradation of rapamycin involving retro-Michael and retro-aldol steps retrieves the entire C1-C27 subunit.