(4R,5S,7R,8R,9R,10S,11S,12S,13S,14R,16S)-13,20-Epoxy-16-ethoxy-11,12-dihydroxypicras-2-en-21-oic acid methyl ester | 155028-25-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (4R,5S,7R,8R,9R,10S,11S,12S,13S,14R,16S)-13,20-Epoxy-16-ethoxy-11,12-dihydroxypicras-2-en-21-oic acid methyl ester
• 英文别名: methyl (1R,2R,4S,6R,8S,9R,13S,14R,15S,16S,17S)-4-ethoxy-15,16-dihydroxy-9,13-dimethyl-5,18-dioxapentacyclo[12.5.0.01,6.02,17.08,13]nonadec-10-ene-17-carboxylate
• CAS: 155028-25-4
• 化学式: C₂₃H₃₄O₇
• 分子量: 422.519
• InChiKey: ZNHBDPHJYSPFIB-IOVNREMPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  30
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  94.4
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (4R,5S,7R,8R,9R,10S,11S,12S,13S,14R,16S)-13,20-Epoxy-16-ethoxy-11,12-dihydroxypicras-2-en-21-oic acid methyl ester 在 二甲基亚砜 、 三氟乙酸酐 作用下， 以 二氯甲烷 为溶剂， 以81.6%的产率得到(4R,5S,7R,8R,9R,10S,12R,13S,14R,16S)-13,20-Epoxy-16-ethoxy-12-hydroxy-11-oxopicras-2-en-21-oic acid methyl ester
  参考文献：
  名称：

  Synthesis of 15-deoxy-16.beta.-ethoxybruceantin and synthetic efforts toward bruceantin

  摘要：

  Utilization of asymmetric Michael addition leads to chiral phenanthrenone (+)-4 suitable for the synthesis of Bruceantin. The D-ring is assembled by means of an intramolecular alkylation of the bromoacetals 25 while only the axial diastereomer 25ax proceeds smoothly. The formation of the cyanohydrin introduces the C-13 carborxyl group and tandem intramolecular alkylation provides the furan E-ring. The C-11,12 cis-diol 39 is readily transformed to the trans-diol 42 via an unusual Swern-type oxidation/reduction sequence. The C-2,3 olefin proves to be an efficient progenitor for the A-ring diosphenol function which can be introduced at the late stage of the synthesis. 15-Deoxy-16 beta-ethoxybruceantin 3 is accordingly prepared. Attempts to elaborate common intermediates toward the synthesis of bruceantin are described. The presence of an oxygen function at C-15 drastically changes the relative reactivity of the C-2,3 and C-11,12 olefinic bonds.

  DOI：

  10.1021/jo00081a008
• 作为产物：
  描述：

  (4R,5S,7R,8R,9R,10S,12S,14R,16S)-20-(Methanesulfonyl)-16-ethoxy-13-oxo-12-(phenylseleno)-21-norpicras-2-ene 在 氢氧化钾 、 四氧化锇 、 18-冠醚-6 、 双氧水 、 碳酸氢钠 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醚 、 二氯甲烷 、 乙腈 为溶剂， 反应 58.25h， 生成 (4R,5S,7R,8R,9R,10S,11S,12S,13S,14R,16S)-13,20-Epoxy-16-ethoxy-11,12-dihydroxypicras-2-en-21-oic acid methyl ester
  参考文献：
  名称：

  Synthesis of 15-deoxy-16.beta.-ethoxybruceantin and synthetic efforts toward bruceantin

  摘要：

  Utilization of asymmetric Michael addition leads to chiral phenanthrenone (+)-4 suitable for the synthesis of Bruceantin. The D-ring is assembled by means of an intramolecular alkylation of the bromoacetals 25 while only the axial diastereomer 25ax proceeds smoothly. The formation of the cyanohydrin introduces the C-13 carborxyl group and tandem intramolecular alkylation provides the furan E-ring. The C-11,12 cis-diol 39 is readily transformed to the trans-diol 42 via an unusual Swern-type oxidation/reduction sequence. The C-2,3 olefin proves to be an efficient progenitor for the A-ring diosphenol function which can be introduced at the late stage of the synthesis. 15-Deoxy-16 beta-ethoxybruceantin 3 is accordingly prepared. Attempts to elaborate common intermediates toward the synthesis of bruceantin are described. The presence of an oxygen function at C-15 drastically changes the relative reactivity of the C-2,3 and C-11,12 olefinic bonds.

  DOI：

  10.1021/jo00081a008

文献信息

• Synthesis of 15-deoxy-16.beta.-ethoxybruceantin and synthetic efforts toward bruceantin
  作者：Charles K.-F. Chiu、S. V. Govindan、P. L. Fuchs

  DOI：10.1021/jo00081a008

  日期：1994.1

  Utilization of asymmetric Michael addition leads to chiral phenanthrenone (+)-4 suitable for the synthesis of Bruceantin. The D-ring is assembled by means of an intramolecular alkylation of the bromoacetals 25 while only the axial diastereomer 25ax proceeds smoothly. The formation of the cyanohydrin introduces the C-13 carborxyl group and tandem intramolecular alkylation provides the furan E-ring. The C-11,12 cis-diol 39 is readily transformed to the trans-diol 42 via an unusual Swern-type oxidation/reduction sequence. The C-2,3 olefin proves to be an efficient progenitor for the A-ring diosphenol function which can be introduced at the late stage of the synthesis. 15-Deoxy-16 beta-ethoxybruceantin 3 is accordingly prepared. Attempts to elaborate common intermediates toward the synthesis of bruceantin are described. The presence of an oxygen function at C-15 drastically changes the relative reactivity of the C-2,3 and C-11,12 olefinic bonds.