16a'-homo-leurosidine | 363623-10-3

• 分子结构分类: 有机化合物 - 生物碱及其衍生物
• 英文名称: 16a'-homo-leurosidine
• 英文别名: methyl (1R,9R,10S,11R,12R,19R)-11-acetyloxy-12-ethyl-4-[(13S,16R,18S)-18-ethyl-18-hydroxy-13-methoxycarbonyl-1,11-diazatetracyclo[14.3.1.04,12.05,10]icosa-4(12),5,7,9-tetraen-13-yl]-10-hydroxy-5-methoxy-8-methyl-8,16-diazapentacyclo[10.6.1.01,9.02,7.016,19]nonadeca-2,4,6,13-tetraene-10-carboxylate
• CAS: 363623-10-3
• 化学式: C₄₇H₆₀N₄O₉
• 分子量: 825.015
• InChiKey: DUXFVCCMVAYXKF-UUGHQEBLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  60
• 可旋转键数：
  10
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  154
• 氢给体数：
  3
• 氢受体数：
  12

反应信息

• 作为产物：
  描述：

  methyl (1R,9R,10S,11R,12R,19R)-11-acetyloxy-4-[(2S,5R)-7-benzyl-5-[(2R)-2-hydroxy-2-(hydroxymethyl)butyl]-2-methoxycarbonyl-7,17-diazatricyclo[8.7.0.011,16]heptadeca-1(10),11,13,15-tetraen-2-yl]-12-ethyl-10-hydroxy-5-methoxy-8-methyl-8,16-diazapentacyclo[10.6.1.01,9.02,7.016,19]nonadeca-2,4,6,13-tetraene-10-carboxylate 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 27.33h， 生成 16a'-homo-leurosidine
  参考文献：
  名称：

  The Syntheses of 16a‘-homo-Leurosidine and 16a‘-homo-Vinblastine. Generation of Atropisomers

  摘要：

  The synthesis of 16a'-homo-leurosidine was achieved through enantioselective generation of a ring U-seco-precursor 33 (without requirement of a chiral auxiliary). Its cyclization provided the N-b'-quaternary salt 35 with a configuration corresponding to the atropisomeric form 8a rather than 8b of the target product. On debenzylation, the amine Sa was obtained and found not to isomerize thermally to the anticipated atropisomer 8b (in contrast to its lower homologue, with its formation of natural leurosidine). However, on protonation, a 1:1 mixture of atropisomers of 16a'-homo-leurosidine was obtained. A synthesis of 16a'-homo-vinblastine provided two atropisomers 5a and 5b for the free base at equilibrium (1:2.3 at room temperature in CDCl3), with a shift to the major conformer 5b with increasing solvent acidity or decreasing temperature. The synthesis was achieved through a stereoselective inversion of the tertiary hydroxyl function in the enantioselectively generated C-20' progenitor 39.

  DOI：

  10.1021/jo000250y