Methyl 5-<2,2-Bis(methylthio)ethyl>-3(E)-ethylidene-1,2,3,4,5,6-hexahydro-2,6-methano<1,4>-diazocino<1,2-a>indole-1β-carboxylate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: Methyl 5-<2,2-Bis(methylthio)ethyl>-3(E)-ethylidene-1,2,3,4,5,6-hexahydro-2,6-methano<1,4>-diazocino<1,2-a>indole-1β-carboxylate
• 英文别名: Methyl 5-[2,2-Bis(methylthio)ethyl]-3(E)-ethylidene-1,2,3,4,5,6-hexahydro-2,6-methano[1,4]-diazocino[1,2-a]indole-1β-carboxylate；methyl (1S,11S,12S,13E)-15-[2,2-bis(methylsulfanyl)ethyl]-13-ethylidene-10,15-diazatetracyclo[10.3.1.02,10.04,9]hexadeca-2,4,6,8-tetraene-11-carboxylate
• 化学式: C₂₂H₂₈N₂O₂S₂
• 分子量: 416.609
• InChiKey: XXORCXMGDVHIIA-DKBHKMMVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  85.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  (+/-)-vinoxine 在 三氟化硼乙醚 、 二甲基亚砜 、 三乙胺 、 三氟乙酸酐 作用下， 以 二氯甲烷 为溶剂， 反应 13.5h， 生成 Methyl 5-<2,2-Bis(methylthio)ethyl>-3(E)-ethylidene-1,2,3,4,5,6-hexahydro-2,6-methano<1,4>-diazocino<1,2-a>indole-1β-carboxylate
  参考文献：
  名称：

  Studies on the synthesis of mavacurine-type indole alkaloids. First total synthesis of (±)-2,7-dihydropleiocarpamine

  摘要：

  Closure of the six-membered C ring of pentacyclic mavacurine-type alkaloids from suitably substituted tetracyclic substructures embodying rings ABDE of these alkaloids, either by electrophilic cyclization upon the indole 3-position or by intramolecular alkylation of the piperidine nitrogen, failed. In contrast, 6a-homopleiocarpamine (45) has been synthesized from dithioacetal 42 by an electrophilic cyclization involving the closure of the seven-membered C ring. The first total synthesis of the alkaloid 2,7-dihydropleiocarpamine (68) has been achieved by photocyclization of the tetracyclic chloroacetamide 54 as the key step. The required tetracyclic ABDE ring systems were prepared by a straightforward sequence consisting of nucleophilic addition of a 1-indoleacetatic ester enolate to the gamma position of a pyridinium salt, acid cyclization of the resulting 1,4-dihydropyridine, and final elaboration of the (E)-ethylidene substituent. An alternative synthesis of the tetracyclic alkaloid vinoxine (10a) is also reported.

  DOI：

  10.1021/jo00079a021

文献信息

• Studies on the synthesis of mavacurine-type indole alkaloids. First total synthesis of (±)-2,7-dihydropleiocarpamine
  作者：M. Lluisa Bennasar、Ester Zulaica、Juan Miguel Jimenez、Joan Bosch

  DOI：10.1021/jo00079a021

  日期：1993.12

  Closure of the six-membered C ring of pentacyclic mavacurine-type alkaloids from suitably substituted tetracyclic substructures embodying rings ABDE of these alkaloids, either by electrophilic cyclization upon the indole 3-position or by intramolecular alkylation of the piperidine nitrogen, failed. In contrast, 6a-homopleiocarpamine (45) has been synthesized from dithioacetal 42 by an electrophilic cyclization involving the closure of the seven-membered C ring. The first total synthesis of the alkaloid 2,7-dihydropleiocarpamine (68) has been achieved by photocyclization of the tetracyclic chloroacetamide 54 as the key step. The required tetracyclic ABDE ring systems were prepared by a straightforward sequence consisting of nucleophilic addition of a 1-indoleacetatic ester enolate to the gamma position of a pyridinium salt, acid cyclization of the resulting 1,4-dihydropyridine, and final elaboration of the (E)-ethylidene substituent. An alternative synthesis of the tetracyclic alkaloid vinoxine (10a) is also reported.