(4R,5S,7R,8R,9R,10S,11R,12S,13S,14R,16S)-11,12-Bis(dichloroacetoxy)-13,20-epoxy-16-ethoxypicras-2-en-21-oic acid methyl ester | 155028-29-8

• 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,11R,12S,13S,14R,16S)-11,12-Bis(dichloroacetoxy)-13,20-epoxy-16-ethoxypicras-2-en-21-oic acid methyl ester
• 英文别名: methyl (1R,2R,4S,6R,8S,9R,13S,14R,15R,16S,17S)-15,16-bis[(2,2-dichloroacetyl)oxy]-4-ethoxy-9,13-dimethyl-5,18-dioxapentacyclo[12.5.0.01,6.02,17.08,13]nonadec-10-ene-17-carboxylate
• CAS: 155028-29-8
• 化学式: C₂₇H₃₄Cl₄O₉
• 分子量: 644.374
• InChiKey: YVWXMWLMMZQPBZ-UYIXNIEMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  40
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  107
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  (4R,5S,7R,8R,9R,10S,11R,12S,13S,14R,16S)-11,12-Bis(dichloroacetoxy)-13,20-epoxy-16-ethoxypicras-2-en-21-oic acid methyl ester 在 吡啶 、 四氧化锇 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 以67.8%的产率得到(2S^*,3R^*,4R^*,5S^*,7R^*,8R^*,9R^*,10S^*,11R^*,12S^*,13S^*,14R^*,16S^*)-11,12-Bis(dichloroacetoxy)-2,3-dihydroxy-13,20-epoxy-16-ethoxypicras-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,12R,13R,14R,16S)-13,20-Epoxy-16-ethoxy-12-(phenylseleno)-21-nitrilopicrasa-2-ene 在 吡啶 、 氢氧化钾 、 四氧化锇 、 双氧水 、 三乙酰氧基硼氢化钠 、 碳酸氢钠 、 二甲基亚砜 、 三氟乙酸酐 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醚 、 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 64.42h， 生成 (4R,5S,7R,8R,9R,10S,11R,12S,13S,14R,16S)-11,12-Bis(dichloroacetoxy)-13,20-epoxy-16-ethoxypicras-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