methyl (3aR,4R,11bR)-3-((Z)-2-iodobut-2-en-1-yl)-2,3,3a,4,5,7-hexahydro-4-acetoxy-1H-pyrrolo[2,3-d]carbazole-6-carboxylate | 204010-31-1

• 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: methyl (3aR,4R,11bR)-3-((Z)-2-iodobut-2-en-1-yl)-2,3,3a,4,5,7-hexahydro-4-acetoxy-1H-pyrrolo[2,3-d]carbazole-6-carboxylate
• 英文别名: methyl (3aR,4R,11bR)-4-acetyloxy-3-[(Z)-2-iodobut-2-enyl]-1,2,3a,4,5,7-hexahydropyrrolo[2,3-d]carbazole-6-carboxylate
• CAS: 204010-31-1
• 化学式: C₂₂H₂₅IN₂O₄
• 分子量: 508.356
• InChiKey: GXFOEOFSPFRCFG-LBFSEVBKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  67.9
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl (3aR,4R,11bR)-3-((Z)-2-iodobut-2-en-1-yl)-2,3,3a,4,5,7-hexahydro-4-acetoxy-1H-pyrrolo[2,3-d]carbazole-6-carboxylate 在 水 、 potassium carbonate 、 二甲基亚砜 、 三乙胺 、 三氟乙酸酐 作用下， 以 甲醇 为溶剂， 反应 3.5h， 生成 (3aR,11bR)-3-((Z)-2-Iodo-but-2-enyl)-4-oxo-2,3,3a,4,5,7-hexahydro-1H-pyrrolo[2,3-d]carbazole-6-carboxylic acid methyl ester
  参考文献：
  名称：

  Application of Ferrocenylalkyl Chiral Auxiliaries to Syntheses of Indolenine Alkaloids:  Enantioselective Syntheses of Vincadifformine, ψ- and 20-epi-ψ-Vincadifformines, Tabersonine, Ibophyllidine, and Mossambine

  摘要：

  Condensations of the chiral N-ferrocenylethylindoloazepines 4a,b, with the aldehydes 5, 13, 19, 29, and 32, led to tetracyclic vinylogous urethanes 6a,b and 7,14a and 14b,21a,c and 21b,d,30a and 31a, and 30b and 31b. Respectively, 6:1, 5:1, 3:1, 1.7:1, and 2:1 diastereomeric selections provided intermediates which, on cleavage of the chiral auxiliary N-substituent and subsequent elaboration of ring D of the Aspidosperma and Strychnos alkaloids, provided enantiomerically pure (-)-psi- and (-)-epi-psi-vincadifformines (1, 2), (+)-ibophyllidine (12), (+)-and (-)-vincadifformine (16a, 16b), (-)-tabersonine (27), and (-)-mossambine (41).

  DOI：

  10.1021/jo971838g
• 作为产物：
  描述：

  (Z)-1-bromo-2-iodo-2-butene 、 (3aR,4R,11bR)-4-Acetoxy-3-(2,2,2-trifluoro-acetyl)-2,3,3a,4,5,7-hexahydro-1H-pyrrolo[2,3-d]carbazole-6-carboxylic acid methyl ester 在 potassium carbonate 作用下， 以 四氢呋喃 为溶剂， 以92%的产率得到methyl (3aR,4R,11bR)-3-((Z)-2-iodobut-2-en-1-yl)-2,3,3a,4,5,7-hexahydro-4-acetoxy-1H-pyrrolo[2,3-d]carbazole-6-carboxylate
  参考文献：
  名称：

  Application of Ferrocenylalkyl Chiral Auxiliaries to Syntheses of Indolenine Alkaloids:  Enantioselective Syntheses of Vincadifformine, ψ- and 20-epi-ψ-Vincadifformines, Tabersonine, Ibophyllidine, and Mossambine

  摘要：

  Condensations of the chiral N-ferrocenylethylindoloazepines 4a,b, with the aldehydes 5, 13, 19, 29, and 32, led to tetracyclic vinylogous urethanes 6a,b and 7,14a and 14b,21a,c and 21b,d,30a and 31a, and 30b and 31b. Respectively, 6:1, 5:1, 3:1, 1.7:1, and 2:1 diastereomeric selections provided intermediates which, on cleavage of the chiral auxiliary N-substituent and subsequent elaboration of ring D of the Aspidosperma and Strychnos alkaloids, provided enantiomerically pure (-)-psi- and (-)-epi-psi-vincadifformines (1, 2), (+)-ibophyllidine (12), (+)-and (-)-vincadifformine (16a, 16b), (-)-tabersonine (27), and (-)-mossambine (41).

  DOI：

  10.1021/jo971838g

文献信息

• New Ferrocenyl Chiral Auxiliary Substituents for Amines. Applications to Syntheses of Mossambine and Vinblastine
  作者：Martin E. Kuehne、Wenning Dai、Yun-Long Li

  DOI：10.1021/jo001399c

  日期：2001.3.1

  (+)-(R)-1,2-(alpha-(R)-Mesyloxy-beta -dimethyltetramethylene)-ferrocene was synthesized and used as a chiral auxiliary for N-alkylation of methyl 1,2,3,4,5,6-hexahydroazepino [4,5-b] indole-5-xi -carboxylates. Condensation with aldehydes then provided tetracyclic products in a diastereomeric ratio of at least 97:3. Gentle cleavage in acetic acid removed the chiral auxiliary to give the corresponding secondary amines in >99% ee. Thus, key intermediates leading to mossambine and vinblastine could be synthesized with high enantioselectivity. The enantioselectivity greatly exceeds that found with other chiral N-auxiliaries developed in our studies.

  (+)-(R)-1,2-(α-(R)-甲磺酰氧基-β-二甲基四亚甲基)二茂铁被成功合成，并作为手性助剂用于N-烷基化甲基1,2,3,4,5,6-六氢氮杂双环[4,5-b]吲哚-5-羧酸酯。与相应的醛进行缩合反应，则生成四环产物，其异构体比例至少达到97:3。在醋酸中进行温和水解可去除手性助剂，获得对应二级胺，其对映体纯度超过99%。因此，利用该方法可高效高选择性地合成莫桑比恩和长春碱的关键中间体。本研究开发的手性N-助剂的对映选择性远超此前研究中所发现的结果。
• Application of Ferrocenylalkyl Chiral Auxiliaries to Syntheses of Indolenine Alkaloids:  Enantioselective Syntheses of Vincadifformine, ψ- and 20-<i>epi</i>-ψ-Vincadifformines, Tabersonine, Ibophyllidine, and Mossambine
  作者：Martin E. Kuehne、Upul K. Bandarage、Abdelhakim Hammach、Yun-Long Li、Tiansheng Wang

  DOI：10.1021/jo971838g

  日期：1998.4.1

  Condensations of the chiral N-ferrocenylethylindoloazepines 4a,b, with the aldehydes 5, 13, 19, 29, and 32, led to tetracyclic vinylogous urethanes 6a,b and 7,14a and 14b,21a,c and 21b,d,30a and 31a, and 30b and 31b. Respectively, 6:1, 5:1, 3:1, 1.7:1, and 2:1 diastereomeric selections provided intermediates which, on cleavage of the chiral auxiliary N-substituent and subsequent elaboration of ring D of the Aspidosperma and Strychnos alkaloids, provided enantiomerically pure (-)-psi- and (-)-epi-psi-vincadifformines (1, 2), (+)-ibophyllidine (12), (+)-and (-)-vincadifformine (16a, 16b), (-)-tabersonine (27), and (-)-mossambine (41).