methyl (1S,12R,19R)-12-ethyl-15-oxo-8,16-diazapentacyclo[10.6.1.01,9.02,7.016,19]nonadeca-2,4,6,9-tetraene-10-carboxylate

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 冬青素型生物碱
• 英文名称: methyl (1S,12R,19R)-12-ethyl-15-oxo-8,16-diazapentacyclo[10.6.1.01,9.02,7.016,19]nonadeca-2,4,6,9-tetraene-10-carboxylate
• 化学式: C₂₁H₂₄N₂O₃
• 分子量: 352.433
• InChiKey: OQLYVMALDCKIQD-NJDAHSKKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  58.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (1S,12R,19R)-12-ethyl-15-oxo-8,16-diazapentacyclo[10.6.1.01,9.02,7.016,19]nonadeca-2,4,6,9-tetraene-10-carboxylate 在 tetraphosphorus decasulfide 、 镍 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 35.0h， 生成 (+)-vincadifformine
  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：

  methyl 1,2,3,4,5,6-hexahydroazepino<4,5-b>indole-5-carboxylate 在 palladium on activated charcoal 氢气 、 N,N-二异丙基乙胺 作用下， 以 溶剂黄146 为溶剂， 反应 24.0h， 生成 methyl (1S,12R,19R)-12-ethyl-15-oxo-8,16-diazapentacyclo[10.6.1.01,9.02,7.016,19]nonadeca-2,4,6,9-tetraene-10-carboxylate
  参考文献：
  名称：

  Studies in biomimetic alkaloid syntheses. 6. Alternative pathways to secodines and their acyclic enamino acrylate analogs. Total syntheses of desethylibophyllidine, D-norvincadifformine, desethylvincadifformine, 20-methyldesethylvincadifformine, and 3-oxovincadifformine

  摘要：

  DOI：

  10.1021/jo00323a007

文献信息

• Total Syntheses of Vincadifformine, 3-Oxovincadifformine, Pseudo- and 20-<i>epi</i>-Pseudovincadifformine, Tabersonine, and Δ¹⁸-Tabersonine through Radical Reactions and Heck Reactions
  作者：Martin E. Kuehne、Tiansheng Wang、Pamela J. Seaton

  DOI：10.1021/jo960607r

  日期：1996.1.1

  The pentacyclic alkaloids vincadifformine (9), psi-vincadifformine (15), and epi-psi-vincadifformine (16) could be synthesized by intramolecular free-radical-induced cyclizations of the tetracyclic intermediates 7, 8, and 18, which were respectively obtained by condensation of the indoloazepine 1 with 2-(phenylselenyl)butyraldehyde and subsequent N-b-alkylation of the resulting tetracyclic amines 2 and 3, or from condensation of (phenylselenyl)acetaldehyde with the alkylated indoloazepine 17. The intermediates 2 and 3 also gave 3-oxovincadifformine (21) by an intermolecular radical alkylation with methyl acrylate. Their alkylation with (Z)-1,3-diiodopropene, phenyl selenoxide elimination, and intramolecular Heck reactions provided tabersonine (24) and 18,19-didehydrotabersonine (27).
• Biomimetic alkaloid syntheses. 15. Enantioselective syntheses with epichlorohydrin: total syntheses of (+)-, (-)- and (.+-.)-vindoline and a synthesis of (-)-vindorosine
  作者：Martin E. Kuehne、David E. Podhorez、Tshilundu Mulamba、William G. Bornmann

  DOI：10.1021/jo00379a006

  日期：1987.2
• Hugel, Georgette; Laronze, Jean-Yves; Laronze, Jacqueline, Heterocycles, 1981, vol. 16, # 4, p. 581 - 590
  作者：Hugel, Georgette、Laronze, Jean-Yves、Laronze, Jacqueline、Levy, Jean

  DOI：——

  日期：——
• Studies in biomimetic alkaloid syntheses. 6. Alternative pathways to secodines and their acyclic enamino acrylate analogs. Total syntheses of desethylibophyllidine, D-norvincadifformine, desethylvincadifformine, 20-methyldesethylvincadifformine, and 3-oxovincadifformine
  作者：Martin E. Kuehne、Thomas H. Matsko、John C. Bohnert、Linda Motyka、David Oliver-Smith

  DOI：10.1021/jo00323a007

  日期：1981.5
• 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).