vincovaline | 220719-29-9

• 分子结构分类: 有机化合物 - 生物碱及其衍生物
• 英文名称: vincovaline
• CAS: 220719-29-9
• 化学式: C₄₆H₅₈N₄O₉
• 分子量: 810.988
• InChiKey: JXLYSJRDGCGARV-LKGYUBROSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.99
• 重原子数：
  59.0
• 可旋转键数：
  7.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  154.1
• 氢给体数：
  3.0
• 氢受体数：
  12.0

反应信息

• 作为产物：
  描述：

  (3aS,4S)-methyl 3-benzyl-2,3,3a,4,5,7-hexahydro-4-<(2R)-2-ethyl-2-<(trimethylsilyl)oxy>-3-<(p-tolylsulfonyl)oxy>propyl>-1H-pyrrolo<2,3-d>carbazole-6-carboxylate 在 四氟硼酸-二乙醚络合物 、 silver tetrafluoroborate 、 钾硼氢 、 次氯酸叔丁酯 、 四丁基氟化铵 、 溶剂黄146 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 为溶剂， 反应 0.92h， 生成 vincovaline
  参考文献：
  名称：

  Enantioselective syntheses of vinblastine, leurosidine, vincovaline and 20'-epi-vincovaline

  摘要：

  The binary indole-indoline alkaloids vinblastine (1), leurosidine (13), 20'-epi-vincovaline (14a), and vincovaline (14b) were obtained by coupling of vindoline (3) to the tetracyclic intermediates 7a, 7b or 22a, 22b, followed by reduction and cyclization steps (60% overall yield for these reactions). The intermediates were obtained by enantioselective establishment of C20' through a first-step Sharpless oxidation (10a,b) and followed by a subsequent diastereomeric separation (20a,b or 21a,b). Alternatively, enantioselective control of the key secodine-type cyclization in the reaction sequence provided the tetracyclic intermediates 54 and 60 for coupling to vindoline. Selective generation of the natural (1, 13, 14a,b) or unnatural (30, 34, 35a,b) atropisomeric forms of the alkaloids was achieved through alternative closures of ring D'. The natural products were also obtained from the higher energy atropisomers by conformational inversion on heating. For the vinblastine synthesis, the overall yield was 22%.

  DOI：

  10.1021/jo00002a008

文献信息

• Circular dichroism studies of bisindole Vinca alkaloids
  作者：Craig A. Parish、Jian-Guo Dong、William G. Bornmann、Joan Chang、Koji Nakanishi、Nina Berova

  DOI：10.1016/s0040-4020(98)00988-0

  日期：1998.12

  The analysis of a series of seventeen vinblastine analogs by circular dichroism is described. Exciton coupling of the indole and indoline chromophores of these compounds provides a general, non-empirical method for the assignment of the C16′ configuration with the bioactive C16′-S and the inactive C16′-R analogs giving rise, respectively, to positive and negative couplets. An analysis of the non-coupled

  描述了通过圆二色性分析一系列十七种长春碱类似物的方法。这些化合物的吲哚和二氢吲哚发色团的激子偶联提供了一种通用的非经验方法，用于分配具有生物活性C16'-S和非活性C16'-R类似物的C16'构型，分别产生正离子和正离子。消极对联。CD的非耦合跃迁的分析表明，尽管经验性的，但305 nm处的正Cotton效应与生物活性有关。还描述了长春碱非对映异构体的UV和CD光谱的理论计算。