(3aR,4S,5S,11bS)-dimethyl 3-benzyl-2,3,3a,4,5,7-hexahydro-4-[(2R)-2-ethyl-2,3-(isopropylidenedioxy)propyl]-1H-pyrrolo[2,3-d]carbazole-5,6-dicarboxylate | 362516-77-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: (3aR,4S,5S,11bS)-dimethyl 3-benzyl-2,3,3a,4,5,7-hexahydro-4-[(2R)-2-ethyl-2,3-(isopropylidenedioxy)propyl]-1H-pyrrolo[2,3-d]carbazole-5,6-dicarboxylate
• 英文别名: dimethyl (3aR,4S,5S,11bS)-3-benzyl-4-[[(4R)-4-ethyl-2,2-dimethyl-1,3-dioxolan-4-yl]methyl]-1,2,3a,4,5,7-hexahydropyrrolo[2,3-d]carbazole-5,6-dicarboxylate
• CAS: 362516-77-6
• 化学式: C₃₃H₄₀N₂O₆
• 分子量: 560.69
• InChiKey: JXTILJHNUCOZKJ-KKFKBBSWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  41
• 可旋转键数：
  9
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  86.3
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (3aR,4S,5S,11bS)-dimethyl 3-benzyl-2,3,3a,4,5,7-hexahydro-4-[(2R)-2-ethyl-2,3-(isopropylidenedioxy)propyl]-1H-pyrrolo[2,3-d]carbazole-5,6-dicarboxylate 在 盐酸 作用下， 以 甲醇 为溶剂， 反应 0.25h， 以99%的产率得到(3aR,4S,5S,11bS)-dimethyl 3-benzyl-2,3,3a,4,5,7-hexahydro-4-[(2R)-2-ethyl-2,3-(dihydroxy)propyl]-1H-pyrrolo[2,3-d]carbazole-5,6-dicarboxylate
  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
• 作为产物：
  描述：

  (4R)-4-ethyl-4,5-dihydroxypentanal acetonide 、 methyl 2-benzyl-1-(2-methoxy-2-oxoethyl)-4,9-dihydro-3H-pyrido[3,4-b]indole-1-carboxylate 在 silica gel 作用下， 反应 3.0h， 生成 (3aR,4S,5S,11bS)-dimethyl 3-benzyl-2,3,3a,4,5,7-hexahydro-4-[(2R)-2-ethyl-2,3-(isopropylidenedioxy)propyl]-1H-pyrrolo[2,3-d]carbazole-5,6-dicarboxylate 、 (3aR,4S,5R,11bS)-dimethyl 3-benzyl-2,3,3a,4,5,7-hexahydro-4-[(2R)-2-ethyl-2,3-(isopropylidenedioxy)propyl]-1H-pyrrolo[2,3-d]carbazole-5,6-dicarboxylate 、 (3aS,4R,5S,11bR)-dimethyl 3-benzyl-2,3,3a,4,5,7-hexahydro-4-[(2R)-2-ethyl-2,3-(isopropylidenedioxy)propyl]-1H-pyrrolo[2,3-d]carbazole-5,6-dicarboxylate 、 (3aS,4R,5R,11bR)-dimethyl 3-benzyl-2,3,3a,4,5,7-hexahydro-4-[(2R)-2-ethyl-2,3-(isopropylidenedioxy)propyl]-1H-pyrrolo[2,3-d]carbazole-5,6-dicarboxylate
  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

文献信息

• The Syntheses of 16a‘-<i>homo-</i>Leurosidine and 16a‘-<i>homo-</i>Vinblastine. Generation of Atropisomers
  作者：Martin E. Kuehne、Yong Qin、Anne E. Huot、Susan L. Bane

  DOI：10.1021/jo000250y

  日期：2001.8.1

  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.