methyl 2-benzyl-4(E)-ethylidene-11-methyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<3,4-b>indole-6β-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 2-benzyl-4(E)-ethylidene-11-methyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<3,4-b>indole-6β-carboxylate
• 英文别名: methyl 2-benzyl-4(E)-ethylidene-11-methyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino[3,4-b]indole-6β-carboxylate；methyl (1R,11R,12S,13E)-15-benzyl-13-ethylidene-3-methyl-3,15-diazatetracyclo[10.3.1.02,10.04,9]hexadeca-2(10),4,6,8-tetraene-11-carboxylate
• 化学式: C₂₆H₂₈N₂O₂
• 分子量: 400.521
• InChiKey: VRYKOGOCGUEPDI-CGPKPQSPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  30
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  34.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 2-benzyl-4(E)-ethylidene-11-methyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<3,4-b>indole-6β-carboxylate 在 三乙基硅烷 、 镍 、 sodium cyanoborohydride 、 间氯过氧苯甲酸 、 三氟乙酸 、 三氟乙酸酐 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 13.5h， 生成 methyl (3RS,4SR,4aSR,9aRS)-12-benzyl-10(E)-ethylidene-9-methyl-13-oxo-1,2,3,4,4a,9a-hexahydro-3,4a-(ethanoiminoethano)carbazole-4-carboxylate
  参考文献：
  名称：

  akuammiline生物碱的合成研究。获取3,4-secoakuammilan衍生物

  摘要：

  tetracycles的C-3 / N-4键的裂解1和6与氯甲酸酯或酰氯，然后还原，导致四氢咔唑4A，4B和图8b-d ，从该二硫12和亚砜5a，5b中，11，和准备了17个。尝试通过DMTSF促进12的环化或通过亚砜5a，b和11的Pummerer环化来构建akuammiline生物碱的四级C-7中心会导致失败，而亚砜17在吲哚的3位上进行环化以生成四环3,4-secoakuammilan型衍生物18。

  DOI：

  10.1016/s0040-4020(99)00070-8
• 作为产物：
  描述：

  甲醇 、 生成 methyl 2-benzyl-4(E)-ethylidene-11-methyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<3,4-b>indole-6α-carboxylate 、 methyl 2-benzyl-4(E)-ethylidene-11-methyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<3,4-b>indole-6β-carboxylate
  参考文献：
  名称：

  Synthetic Efforts toward Akuammiline Alkaloids from Tetracyclic 6,7-Seco Derivatives

  摘要：

  The addition of enolates derived from indole-3-acetic esters 1-3 to pyridinium salts 4, 23, and 24, followed by acid cyclization of the resulting 1,4-dihydropyridines, leads to tetrahydro-1,5-methanoazocino[3,4-b]indoles 5-7, 25-27, which have been subsequently elaborated into 4E-ethylidene(or 4 alpha-ethyl)-hexahydro-1,5-methanoazocino[3,4-b]indoles. Closure of the six-membered C ring of akuammiline alkaloids by formation of C-6/C-7 bond from appropriately N-(b)-substituted derivatives of these tetracyclic ABDE substructures has been extensively investigated. In the N-unsubstituted indole series, both cyclization of thionium ions generated either by Pummerer reaction from sulfoxide 16 or by DMTSF treatment of dithioacetal 36 and photocyclization of chloroacetamide 47 occur upon the indole nitrogen to give pentacycles 18, 38, and 49, respectively. When the indole nitrogen is blocked by a substituent, the thionium ions derived from sulfoxides 17 and 43 and dithioacetals 37 and 44 do not cyclize and lead to different products depending on the reaction conditions, whereas chloroacetamides 48 and 51 undergo a reductive photodehalogenation. Attempted radical cyclization of seleno derivatives 53, 55, and 56 under a variety of conditions gives the corresponding reduced products. Finally, attempted photoisomerization of 1-acylindole 62 leads to the N-(b)-methyl tetracycle 63.

  DOI：

  10.1021/jo951456f

文献信息

• Construction of the quaternary C-7 centre of akuammiline alkaloids. Synthesis of 3,4-secoakuammilan derivatives
  作者：M.-Lluïsa Bennasar、Ester Zulaica、Antonio Ramírez、Joan Bosch

  DOI：10.1016/0040-4039(96)01412-8

  日期：1996.9

  The first synthesis of 3,4-secoakuammilan derivatives is reported, the key step being the formation of the quaternary C-7 centre by Pummerer cyclization of tetrahydrocarbazole sulfoxide 4.

  据报道，首次合成了3,4-secoakuammilan衍生物，关键步骤是通过四甲基咔唑亚砜4的Pummerer环化反应形成C-7季中心。
• Formation of a Ten-membered Lactam by Chloroacetamide Photocyclization on the Indole 4-Position
  作者：Joan Bosch、M.-LLuïsa Bennasar、Ester Zulaica、Antonio Ramírez

  DOI：10.3987/com-96-7533

  日期：——