dimethyl (20α)-15,16-didehydro-17-oxoyohimban-1,16-dicarboxylate | 132672-71-0

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 柯楠因类生物碱
• 英文名称: dimethyl (20α)-15,16-didehydro-17-oxoyohimban-1,16-dicarboxylate
• CAS: 132672-71-0；132747-34-3
• 化学式: C₂₃H₂₄N₂O₅
• 分子量: 408.454
• InChiKey: YXNLXNQENROIDX-ACJLOTCBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.01
• 重原子数：
  30.0
• 可旋转键数：
  1.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  77.84
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为产物：
  描述：

  N-[2-(1H-吲哚-3-基)乙基]甲酰胺 在 盐酸 、 4-二甲氨基吡啶 、 1,4-diazabicyclo[5.4.0]-7-undecene 、 次氯酸叔丁酯 、 水 、 铜 、 溶剂黄146 、 锌 、 三氯氧磷 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 6.14h， 生成 dimethyl (20α)-15,16-didehydro-17-oxoyohimban-1,16-dicarboxylate
  参考文献：
  名称：

  Total syntheses of yohimbe alkaloids, with stereoselection for the normal, allo, and 3-epiallo series, based on annelations of 4-methoxy-1,2-dihydropyridones

  摘要：

  N-[2-(1H-3-indolyl)ethyl]-2,3-dihydro-4-pyridone (31) was generated in two steps (77% yield) from tryptamine and N-methyl-4-piperidone methiodide. Its cyclization (90% yield) and oxidation (91% yield) provided the tetracyclic analogue 32. O-Methylation and Robinson-type annelation of these vinylogous lactams (the latter in form of its N(a)-carbamate) furnished the dienones 38 (64%) and 43 (90%). Further elaboration by cyclization and/or reduction reactions selectively provided the 15,16-didehydroyohimbinones 7 or 44. Their reductions then led to yohimbinone (52, 20% overall yield from tryptamine), alloyohimbinone (11, 19% overall yield), and 3-epi-alloyohimbinone (10, 23% overall yield), which led to yohimbine (3), beta-yohimbine (9), 3-epi-alloyohimbine (53), and 3-epi-17-epi-alloyohimbine (54).

  DOI：

  10.1021/jo00008a025

文献信息

• Total syntheses of yohimbe alkaloids, with stereoselection for the normal, allo, and 3-epiallo series, based on annelations of 4-methoxy-1,2-dihydropyridones
  作者：Martin E. Kuehne、Randy S. Muth

  DOI：10.1021/jo00008a025

  日期：1991.4

  N-[2-(1H-3-indolyl)ethyl]-2,3-dihydro-4-pyridone (31) was generated in two steps (77% yield) from tryptamine and N-methyl-4-piperidone methiodide. Its cyclization (90% yield) and oxidation (91% yield) provided the tetracyclic analogue 32. O-Methylation and Robinson-type annelation of these vinylogous lactams (the latter in form of its N(a)-carbamate) furnished the dienones 38 (64%) and 43 (90%). Further elaboration by cyclization and/or reduction reactions selectively provided the 15,16-didehydroyohimbinones 7 or 44. Their reductions then led to yohimbinone (52, 20% overall yield from tryptamine), alloyohimbinone (11, 19% overall yield), and 3-epi-alloyohimbinone (10, 23% overall yield), which led to yohimbine (3), beta-yohimbine (9), 3-epi-alloyohimbine (53), and 3-epi-17-epi-alloyohimbine (54).