O-((3R,5S,8R,9S,10S,13S,14S,17S)-3-((tert-butyldimethylsilyl)oxy)-17-(1-chloroisoquinolin-7-yl)-10,13-dimethylhexadecahydro-1H-cyclopenta[a]phenanthren-17-yl) phenylcarbamothioate | 1170704-52-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: O-((3R,5S,8R,9S,10S,13S,14S,17S)-3-((tert-butyldimethylsilyl)oxy)-17-(1-chloroisoquinolin-7-yl)-10,13-dimethylhexadecahydro-1H-cyclopenta[a]phenanthren-17-yl) phenylcarbamothioate
• CAS: 1170704-52-5
• 化学式: C₄₁H₅₅ClN₂O₂SSi
• 分子量: 703.504
• InChiKey: XGOLBZKINBNKDX-YBCUEOQYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.93
• 重原子数：
  48.0
• 可旋转键数：
  5.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  43.38
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  O-((3R,5S,8R,9S,10S,13S,14S,17S)-3-((tert-butyldimethylsilyl)oxy)-17-(1-chloroisoquinolin-7-yl)-10,13-dimethylhexadecahydro-1H-cyclopenta[a]phenanthren-17-yl) phenylcarbamothioate 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 甲苯 为溶剂， 反应 3.5h， 以81%的产率得到tert-butyl-[[(3R,5S,8R,9S,10S,13S,14S,17S)-17-isoquinolin-7-yl-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl]oxy]-dimethylsilane
  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：

  (3R,10S,13S)-3-((tert-butyldimethylsilyl)oxy)-10,13-dimethylhexadecahydro-17H-cyclopenta[a]phenanthren-17-one 在 正丁基锂 、 cerium(III) chloride 、 potassium hydride 作用下， 以 四氢呋喃 、 正己烷 、 mineral oil 为溶剂， 反应 1.5h， 生成 O-((3R,5S,8R,9S,10S,13S,14S,17S)-3-((tert-butyldimethylsilyl)oxy)-17-(1-chloroisoquinolin-7-yl)-10,13-dimethylhexadecahydro-1H-cyclopenta[a]phenanthren-17-yl) phenylcarbamothioate
  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。