methyl (+/-)-(3aR*,4R*,11bR*)-3-(2-bromoallyl)-2,3,3a,4,5,7-hexahydro-4-ethyl-4-(phenylselenyl)-1H-pyrrolo[2,3-d]carbazole-6-carboxylate

• 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-(2-bromoallyl)-2,3,3a,4,5,7-hexahydro-4-ethyl-4-(phenylselenyl)-1H-pyrrolo[2,3-d]carbazole-6-carboxylate
• 英文别名: methyl 3-(2-bromoprop-2-enyl)-4-ethyl-4-phenylselanyl-2,3a,5,7-tetrahydro-1H-pyrrolo[2,3-d]carbazole-6-carboxylate
• 化学式: C₂₇H₂₉BrN₂O₂Se
• 分子量: 572.403
• InChiKey: SVRSDZXLKAKQFY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.76
• 重原子数：
  33.0
• 可旋转键数：
  6.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  41.57
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  methyl (+/-)-(3aR*,4R*,11bR*)-3-(2-bromoallyl)-2,3,3a,4,5,7-hexahydro-4-ethyl-4-(phenylselenyl)-1H-pyrrolo[2,3-d]carbazole-6-carboxylate 在 偶氮二异丁腈 、 三正丁基氢锡 、 三乙胺 作用下， 以 苯 为溶剂， 反应 3.0h， 以71%的产率得到(+)-vincadifformine
  参考文献：
  名称：

  Total Syntheses of Vincadifformine, 3-Oxovincadifformine, Pseudo- and 20-epi-Pseudovincadifformine, Tabersonine, and Δ¹⁸-Tabersonine through Radical Reactions and Heck Reactions

  摘要：

  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).

  DOI：

  10.1021/jo960607r
• 作为产物：
  描述：

  methyl 1,2,3,4,5,6-hexahydroazepino<4,5-b>indole-5-carboxylate 在 potassium carbonate 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 66.0h， 生成 methyl (+/-)-(3aR*,4R*,11bR*)-3-(2-bromoallyl)-2,3,3a,4,5,7-hexahydro-4-ethyl-4-(phenylselenyl)-1H-pyrrolo[2,3-d]carbazole-6-carboxylate
  参考文献：
  名称：

  Total Syntheses of Vincadifformine, 3-Oxovincadifformine, Pseudo- and 20-epi-Pseudovincadifformine, Tabersonine, and Δ¹⁸-Tabersonine through Radical Reactions and Heck Reactions

  摘要：

  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).

  DOI：

  10.1021/jo960607r