1-phenylthiomethyl-2-propionyl-2,3-dihydro-1H-isoindole

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: 1-phenylthiomethyl-2-propionyl-2,3-dihydro-1H-isoindole
• 英文别名: 1-[1-(Phenylsulfanylmethyl)-1,3-dihydroisoindol-2-yl]propan-1-one
• 化学式: C₁₈H₁₉NOS
• 分子量: 297.421
• InChiKey: BHKYIFBHVGWNBR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  45.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  邻溴苄胺 在 偶氮二异丁腈 、 三正丁基氢锡 、 magnesium sulfate 、 N,N-二乙基苯胺 作用下， 以 乙醚 、 苯 为溶剂， 反应 21.5h， 生成 1-phenylthiomethyl-2-propionyl-2,3-dihydro-1H-isoindole
  参考文献：
  名称：

  Total Synthesis of Mappicine Ketone (Nothapodytine B) by Means of Sulfur-Directed 5-exo-Selective Aryl Radical Cyclization onto Enamides

  摘要：

  Enamides 5, on treatment with Bu3SnH-AIBN, underwent aryl radical cyclization in a 5-exo manner to give 1-[bis(phenylthio)methyl]dihydroisoindoles 6, which were partially desulfurized with Bu3SnH-AIBN to give 1-mono(phenylthio)methyl congeners 7. Formation of 6 from 5 may be explained by the presence of two phenylthio groups at the terminus of the N-vinylic bond of 5, since enamide Sa having no phenylthio group underwent aryl radical cyclization in a 6-endo manner. Compound 7d (R = CF3) was transformed into sulfoxide 16, which was treated with (CF3CO)(2)O and then with 10% NaOH to give a model compound 20 of mappicine ketone (MPK) (1) through aldol condensation of aldehyde 18. An attempt to synthesize MPK using this method with sulfoxide 28 prepared from 25, however, was unsuccessful, and, instead, photochemical cyclization of enamide 38 prepared from 25 furnished MPK.

  DOI：

  10.1021/jo030177m

文献信息

• Synthesis of a model compound of mappicine ketone based on sulfur-directed 5-exo selective aryl radical cyclization onto enamides
  作者：Hiroyuki Ishibashi、Issei Kato、Yoshifumi Takeda、Osamu Tamura

  DOI：10.1016/s0040-4039(00)02138-9

  日期：2001.1

  Enamides 10, upon treatment with Bu3SnH-AIBN, gave 5-exo aryl radical cyclization products 11, which were partially desulfurized to give 1-substituted dihydroisoindoles 7 and 12. This method was applied to the synthesis of a model compound 4 of mappicine ketone (1). (C) 2001 Elsevier Science Ltd. All rights reserved.
• Total Synthesis of Mappicine Ketone (Nothapodytine B) by Means of Sulfur-Directed 5-<i>exo</i>-Selective Aryl Radical Cyclization onto Enamides
  作者：Issei Kato、Masayuki Higashimoto、Osamu Tamura、Hiroyuki Ishibashi

  DOI：10.1021/jo030177m

  日期：2003.10.1

  Enamides 5, on treatment with Bu3SnH-AIBN, underwent aryl radical cyclization in a 5-exo manner to give 1-[bis(phenylthio)methyl]dihydroisoindoles 6, which were partially desulfurized with Bu3SnH-AIBN to give 1-mono(phenylthio)methyl congeners 7. Formation of 6 from 5 may be explained by the presence of two phenylthio groups at the terminus of the N-vinylic bond of 5, since enamide Sa having no phenylthio group underwent aryl radical cyclization in a 6-endo manner. Compound 7d (R = CF3) was transformed into sulfoxide 16, which was treated with (CF3CO)(2)O and then with 10% NaOH to give a model compound 20 of mappicine ketone (MPK) (1) through aldol condensation of aldehyde 18. An attempt to synthesize MPK using this method with sulfoxide 28 prepared from 25, however, was unsuccessful, and, instead, photochemical cyclization of enamide 38 prepared from 25 furnished MPK.