7-[(1'S,2'R,5'S,6'R,16'S)-6'-methylspiro[1,3-dioxolane-2,12'-19-oxapentacyclo[14.2.1.01,9.02,6.011,16]nonadeca-8,10-diene]-5'-yl]isoquinoline | 1170704-50-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异喹啉及其衍生物
• 英文名称: 7-[(1'S,2'R,5'S,6'R,16'S)-6'-methylspiro[1,3-dioxolane-2,12'-19-oxapentacyclo[14.2.1.01,9.02,6.011,16]nonadeca-8,10-diene]-5'-yl]isoquinoline
• CAS: 1170704-50-3
• 化学式: C₃₀H₃₃NO₃
• 分子量: 455.597
• InChiKey: PYXBOBIXBYWNKV-PMCIJNRMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  34
• 可旋转键数：
  1
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  40.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  7-[(1'S,2'R,5'S,6'R,16'S)-6'-methylspiro[1,3-dioxolane-2,12'-19-oxapentacyclo[14.2.1.01,9.02,6.011,16]nonadeca-8,10-diene]-5'-yl]isoquinoline 在 lithium aluminium tetrahydride 、 对甲苯磺酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 、 水 、 丙酮 为溶剂， 反应 30.67h， 生成 2-deoxycortistatin A
  参考文献：
  名称：

  Total Synthesis of Cortistatins A and J

  摘要：

  This paper describes the details of our synthetic studies on the marine steroidal alkaloids cortistatins A and J. The key features of our strategy include (i) an efficient Knoevenagel/electrocyclic strategy to couple the diketone and the CD-ring fragment, (ii) a chemoselective radical cyclization to construct the oxabicyclo[3.2.1]octene B-ring system, (iii) a highly stereocontrolled installation of the isoquinoline unit, and (iv) a late-stage functionalization of the A-ring.

  DOI：

  10.1021/jo2002616
• 作为产物：
  描述：

  (1'S,2'R,5'S,6'S,16'S)-5'-(1-chloroisoquinolin-7-yl)-6'-methylspiro[1,3-dioxolane-2,12'-19-oxapentacyclo[14.2.1.01,9.02,6.011,16]nonadeca-8,10-diene]-5'-ol 在 偶氮二异丁腈 、 三正丁基氢锡 、 potassium hydride 作用下， 以 四氢呋喃 、 甲苯 、 mineral oil 为溶剂， 反应 7.5h， 生成 7-[(1'S,2'R,5'S,6'R,16'S)-6'-methylspiro[1,3-dioxolane-2,12'-19-oxapentacyclo[14.2.1.01,9.02,6.011,16]nonadeca-8,10-diene]-5'-yl]isoquinoline
  参考文献：
  名称：

  Total Synthesis of Cortistatins A and J

  摘要：

  This paper describes the details of our synthetic studies on the marine steroidal alkaloids cortistatins A and J. The key features of our strategy include (i) an efficient Knoevenagel/electrocyclic strategy to couple the diketone and the CD-ring fragment, (ii) a chemoselective radical cyclization to construct the oxabicyclo[3.2.1]octene B-ring system, (iii) a highly stereocontrolled installation of the isoquinoline unit, and (iv) a late-stage functionalization of the A-ring.

  DOI：

  10.1021/jo2002616

文献信息

• Efficient and stereoselective installation of isoquinoline: formal total synthesis of cortistatin A
  作者：Shuji Yamashita、Kazuki Kitajima、Kentaro Iso、Masahiro Hirama

  DOI：10.1016/j.tetlet.2009.02.038

  日期：2009.7

  stereoselective attachment of isoquinoline onto the steroidal framework of cortistatin A has been achieved. Our strategy features a Ce-mediated nucleophilic addition of an isoquinoline unit to the sterically congested ketone followed by formation of the phenyl thiocarbamate, and subsequent stereoselective radical reduction. The new method results in a formal total synthesis of cortistatin A.

  已经实现了异喹啉在cortistatin A的甾体骨架上的高度立体选择性连接。我们的策略的特征是将Cequin介导的异喹啉单元亲核加成到空间拥挤的酮中，然后形成苯基硫代氨基甲酸酯，然后进行立体选择性自由基还原。新方法导致了皮质抑素A的正式全合成。