dimethyl 3-<(S)-1-(1-naphthyl)ethyl>-1,2,3,4,5,6-hexahydroazepino<4,5-b>indole-5,5-dicarboxylate | 131703-82-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - Pyrroloazepines
• 英文名称: dimethyl 3-<(S)-1-(1-naphthyl)ethyl>-1,2,3,4,5,6-hexahydroazepino<4,5-b>indole-5,5-dicarboxylate
• 英文别名: dimethyl 3-[(1S)-1-naphthalen-1-ylethyl]-1,2,4,6-tetrahydroazepino[4,5-b]indole-5,5-dicarboxylate
• CAS: 131703-82-7
• 化学式: C₂₈H₂₈N₂O₄
• 分子量: 456.541
• InChiKey: BASRHPZPIUTGNA-SFHVURJKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  34
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  71.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dimethyl 3-<(S)-1-(1-naphthyl)ethyl>-1,2,3,4,5,6-hexahydroazepino<4,5-b>indole-5,5-dicarboxylate 在 盐酸 、 三乙胺盐酸盐 、 三乙胺 、 lithium chloride 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基乙酰胺 、 甲苯 为溶剂， 反应 61.83h， 生成 (7S,5R)-methyl 3-<(S)-1-(1-naphthyl)ethyl>-1,2,3,4,5,6,7,8-octahydro-5-<(2S)-2-ethyl-2,3-epoxypropyl>-7-(15-vindolinyl)azonino<5,4-b>indole-7-carboxylate
  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
• 作为产物：
  描述：

  9b-Chloro-2-((S)-1-naphthalen-1-yl-ethyl)-2,3,4,9b-tetrahydro-1H-pyrido[4,3-b]indole 、 thallium dimethyl malonate 以 四氢呋喃 为溶剂， 生成 dimethyl 3-<(S)-1-(1-naphthyl)ethyl>-1,2,3,4,5,6-hexahydroazepino<4,5-b>indole-5,5-dicarboxylate
  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

• KUEHNE, MARTIN E.;MATSON, PATRICIA A.;BORNMANN, WILLIAM G., J. ORG. CHEM., 56,(1991) N, C. 513-528
  作者：KUEHNE, MARTIN E.、MATSON, PATRICIA A.、BORNMANN, WILLIAM G.

  DOI：——

  日期：——
• Enantioselective syntheses of vinblastine, leurosidine, vincovaline and 20'-epi-vincovaline
  作者：Martin E. Kuehne、Patricia A. Matson、William G. Bornmann

  DOI：10.1021/jo00002a008

  日期：1991.1

  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%.