methyl 4(E)-ethylidene-2-<2-(phenylthio)ethyl>-11-(methoxycarbonyl)-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 4(E)-ethylidene-2-<2-(phenylthio)ethyl>-11-(methoxycarbonyl)-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<3,4-b>indole-6β-carboxylate
• 英文别名: dimethyl (1S,11S,12R,13E)-13-ethylidene-15-(2-phenylsulfanylethyl)-3,15-diazatetracyclo[10.3.1.02,10.04,9]hexadeca-2(10),4,6,8-tetraene-3,11-dicarboxylate
• 化学式: C₂₈H₃₀N₂O₄S
• 分子量: 490.623
• InChiKey: BCQLERMZUWTLOV-PFUGZAQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  35
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  86.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 4(E)-ethylidene-2-<2-(phenylthio)ethyl>-11-(methoxycarbonyl)-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<3,4-b>indole-6β-carboxylate 在 三乙基硅烷 、 三氟乙酸 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 2.25h， 生成 methyl trans-3-<1--1(E)-propenyl>-9-methoxycarbonyl-1,2,3,4-tetrahydrocarbazole-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：

  甲基吲哚-3-乙酸盐 在 盐酸 、 sodium hydride 、 甲基磺酰氯 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 苯 为溶剂， 反应 11.25h， 生成 methyl 4(E)-ethylidene-2-<2-(phenylthio)ethyl>-11-(methoxycarbonyl)-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

• Synthetic Efforts toward Akuammiline Alkaloids from Tetracyclic 6,7-Seco Derivatives
  作者：M.-Lluïsa Bennasar、Ester Zulaica、Antonio Ramírez、Joan Bosch

  DOI：10.1021/jo951456f

  日期：1996.1.1

  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.
• Studies on the synthesis of akuammiline alkaloids. Access to 3,4-secoakuammilan derivatives
  作者：M.-Lluïsa Bennasar、Ester Zulaica、Antonio Ramírez、Joan Bosch

  DOI：10.1016/s0040-4020(99)00070-8

  日期：1999.3

  11, and 17 were prepared. Whereas attempts to construct the quaternary C-7 centre of akuammiline alkaloids either by DMTSF-promoted cyclization of 12 or by Pummerer cyclization of sulfoxides 5a,b and 11 resulted in failure, sulfoxide 17 underwent cyclization on the indole 3-position to give the tetracyclic 3,4-secoakuammilan-type derivative 18.

  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。