3-acetyl-1-methyl-4-{2-[1-(phenylsulfonyl)-2-indolyl]-2-(trichloroacetoxy)vinyl}-5-(trichloroacetyl)-1,4-dihydropyridine

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-acetyl-1-methyl-4-{2-[1-(phenylsulfonyl)-2-indolyl]-2-(trichloroacetoxy)vinyl}-5-(trichloroacetyl)-1,4-dihydropyridine
• 英文别名: [(E)-2-[3-acetyl-1-methyl-5-(2,2,2-trichloroacetyl)-4H-pyridin-4-yl]-1-[1-(benzenesulfonyl)indol-2-yl]ethenyl] 2,2,2-trichloroacetate
• 化学式: C₂₈H₂₀Cl₆N₂O₆S
• 分子量: 725.261
• InChiKey: WXWSOJGKLCJVRC-ZMOGYAJESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  43
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  111
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  3-acetyl-1-methylpyridinium iodide 、 (1-phenylsulfonyl-1H-indol-2-yl)ethanone 、 三氯乙酸酐 在 lithium diisopropyl amide 作用下， 生成 3-acetyl-1-methyl-4-({[1-(phenylsulfonyl)-2-indolyl]carbonyl}methyl)-5-(trichloroacetyl)-1,4-dihydropyridine 、 3-acetyl-1-methyl-4-{2-[1-(phenylsulfonyl)-2-indolyl]-2-(trichloroacetoxy)vinyl}-5-(trichloroacetyl)-1,4-dihydropyridine
  参考文献：
  名称：

  Biomimetic Total Synthesis of Ervitsine and Indole Alkaloids of the Ervatamine Group via 1,4-Dihydropyridines

  摘要：

  Addition of the enolate derived from 2-acetylindole In to pyridinium salt 2 followed by in situ trapping of the initially formed 1,4-dihydropyridine 3a with Eschenmoser's salt gives tetracycle 5a. Subsequent elaboration of the exocyclic methylene and E-ethylidene substituents leads to N-a-methylervitsine (17a). A similar sequence from the N-a-protected 2-acetylindole Ic establishes the first total synthesis of the 2-acylindole alkaloid ervitsine. Alternatively, dihydropyridine 3a is trapped with BrSePh to give the tetracyclic selenide 7a, which is then converted to N-a-methylervitsine by way of selenoxide 20. The synthesis of the alkaloids of the ervatamine group starts with the addition of the enolate derived from 2-acetyl-1-benzylindole (Ig) to pyridinium salt 24 and the conversion of the resulting 1,4-dihydropyridine to 3,5-diacylated dihydropyridine 26g. Chemoselective reduction of the vinylogous amide moiety of 26g, followed by deprotection of the indole ring and LiEt3BH reduction leads to diol 37b. On sequential treatment with Eschenmoser's salt, methyl iodide, NaCNBH3, and MnO2, 37b is converted to the tetracyclic 2-acylindole 39, from which the first total synthesis of 19,20-didehydroervatamine and 20-epiervatamine is accomplished by manipulation of the l-hydroxyethyl chain. The above syntheses can be considered as biomimetic, as cyclization of the key intermediates I and II mimics the key steps of the biosynthesis of the title alkaloids.

  DOI：

  10.1021/jo9623301

文献信息

• Biomimetic Total Synthesis of Ervitsine and Indole Alkaloids of the Ervatamine Group <i>via</i> 1,4-Dihydropyridines
  作者：M.-Lluïsa Bennasar、Bernat Vidal、Joan Bosch

  DOI：10.1021/jo9623301

  日期：1997.5.1

  Addition of the enolate derived from 2-acetylindole In to pyridinium salt 2 followed by in situ trapping of the initially formed 1,4-dihydropyridine 3a with Eschenmoser's salt gives tetracycle 5a. Subsequent elaboration of the exocyclic methylene and E-ethylidene substituents leads to N-a-methylervitsine (17a). A similar sequence from the N-a-protected 2-acetylindole Ic establishes the first total synthesis of the 2-acylindole alkaloid ervitsine. Alternatively, dihydropyridine 3a is trapped with BrSePh to give the tetracyclic selenide 7a, which is then converted to N-a-methylervitsine by way of selenoxide 20. The synthesis of the alkaloids of the ervatamine group starts with the addition of the enolate derived from 2-acetyl-1-benzylindole (Ig) to pyridinium salt 24 and the conversion of the resulting 1,4-dihydropyridine to 3,5-diacylated dihydropyridine 26g. Chemoselective reduction of the vinylogous amide moiety of 26g, followed by deprotection of the indole ring and LiEt3BH reduction leads to diol 37b. On sequential treatment with Eschenmoser's salt, methyl iodide, NaCNBH3, and MnO2, 37b is converted to the tetracyclic 2-acylindole 39, from which the first total synthesis of 19,20-didehydroervatamine and 20-epiervatamine is accomplished by manipulation of the l-hydroxyethyl chain. The above syntheses can be considered as biomimetic, as cyclization of the key intermediates I and II mimics the key steps of the biosynthesis of the title alkaloids.