methyl 4-[2-(1-indolyl)-2-oxoethyl]-1-[2-(phenylsulfanyl)ethyl]-1,4-dihydro-pyridine-3(E)-acrylate | 185824-03-7

• 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-[2-(1-indolyl)-2-oxoethyl]-1-[2-(phenylsulfanyl)ethyl]-1,4-dihydro-pyridine-3(E)-acrylate
• 英文别名: methyl (E)-3-[4-(2-indol-1-yl-2-oxoethyl)-1-(2-phenylsulfanylethyl)-4H-pyridin-3-yl]prop-2-enoate
• CAS: 185824-03-7
• 化学式: C₂₇H₂₆N₂O₃S
• 分子量: 458.581
• InChiKey: ARXWSVXGKXDCDA-VAWYXSNFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  33
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  76.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 4-[2-(1-indolyl)-2-oxoethyl]-1-[2-(phenylsulfanyl)ethyl]-1,4-dihydro-pyridine-3(E)-acrylate 在 盐酸 、 sodium tetrahydroborate 、 偶氮二异丁腈 、 三氟甲磺酸三甲基硅酯 、 三正丁基氢锡 、 sodium methylate 、 对甲苯磺酸 、 N,N-二异丙基乙胺 、 间氯过氧苯甲酸 、 三氟乙酸 、 lithium iodide 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 13.25h， 生成 (+/-)-deformylgeissoschizine
  参考文献：
  名称：

  简洁，立体选择性地合成（±）-Geissoschizine

  摘要：

  （±）-geissoschizine的立体控制合成，包括在吡啶鎓盐2中添加衍生自1-乙酰吲哚的烯醇盐，环合的1,4-二氢吡啶，E-亚乙基取代基的立体选择性修饰，C环的封闭据报道有Pummerer反应和所得五环内酰胺的甲醇分解。

  DOI：

  10.1016/s0040-4039(96)02097-7
• 作为产物：
  描述：

  苯基溴代乙基硫醚 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 生成 methyl 4-[2-(1-indolyl)-2-oxoethyl]-1-[2-(phenylsulfanyl)ethyl]-1,4-dihydro-pyridine-3(E)-acrylate
  参考文献：
  名称：

  Nucleophilic Addition of 1-Acetylindole Enolates to Pyridinium Salts. Stereoselective Formal Synthesis of (±)-Geissoschizine and (±)-Akagerine via 1,4-Dihydropyridines

  摘要：

  Addition of the enolate derived from 1-acetylindole (3) to pyridinium salt 4b followed by acid-induced cyclization of the resulting 1,4-dihydropyridine 5b in the presence of lithium iodide gives tetracyclic 3,7-methano[1,4]diazonino[1,2-alpha]indole 6b, which has subsequently been elaborated into the (E)-ethylidene derivative 7b. From this compound is reported a stereocontrolled route to (+/-)-geissoschizine, involving closure of C ring by Pummerer reaction, methanolysis of the resulting pentacyclic lactam 12, and desulfurization. A similar synthetic sequence starting from the enolate of 3 and 2-fluoropyridinium salt 15b gives access to the pentacyclic dilactam 2, which had previously been converted to (+/-)-akagerine through opening of the piperidone (D) ring.

  DOI：

  10.1021/jo9911894

文献信息

• Nucleophilic Addition of 1-Acetylindole Enolates to Pyridinium Salts. Stereoselective Formal Synthesis of (±)-Geissoschizine and (±)-Akagerine via 1,4-Dihydropyridines
  作者：M.-Lluïsa Bennasar、Juan-Miguel Jiménez、Bernat Vidal、Bilal A. Sufi、Joan Bosch

  DOI：10.1021/jo9911894

  日期：1999.12.1

  Addition of the enolate derived from 1-acetylindole (3) to pyridinium salt 4b followed by acid-induced cyclization of the resulting 1,4-dihydropyridine 5b in the presence of lithium iodide gives tetracyclic 3,7-methano[1,4]diazonino[1,2-alpha]indole 6b, which has subsequently been elaborated into the (E)-ethylidene derivative 7b. From this compound is reported a stereocontrolled route to (+/-)-geissoschizine, involving closure of C ring by Pummerer reaction, methanolysis of the resulting pentacyclic lactam 12, and desulfurization. A similar synthetic sequence starting from the enolate of 3 and 2-fluoropyridinium salt 15b gives access to the pentacyclic dilactam 2, which had previously been converted to (+/-)-akagerine through opening of the piperidone (D) ring.
• A concise, stereoselective synthesis of (±)-geissoschizine
  作者：M.-Lluïsa Bennasar、Juan-Miguel Jiménez、Bilal A. Sufi、Joan Bosch

  DOI：10.1016/s0040-4039(96)02097-7

  日期：1996.12

  A stereocontrolled synthesis of (±)-geissoschizine, involving the addition of the enolate derived from 1-acetylindole to pyridinium salt 2, cyclization of the resultant 1,4-dihydropyridine, stereoselective elaboration of the E-ethylidene substituent, closure of C ring by Pummerer reaction, and methanolysis of the resulting pentacyclic lactam, is reported.

  （±）-geissoschizine的立体控制合成，包括在吡啶鎓盐2中添加衍生自1-乙酰吲哚的烯醇盐，环合的1,4-二氢吡啶，E-亚乙基取代基的立体选择性修饰，C环的封闭据报道有Pummerer反应和所得五环内酰胺的甲醇分解。