1-[2-(3,4-Dimethoxy-phenyl)-ethyl]-6-ethylsulfanyl-7a-hydroxy-2,5-dioxo-1,2,3,4,5,7a-hexahydro-indole-3a-carboxylic acid methyl ester | 202391-96-6

• 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: 1-[2-(3,4-Dimethoxy-phenyl)-ethyl]-6-ethylsulfanyl-7a-hydroxy-2,5-dioxo-1,2,3,4,5,7a-hexahydro-indole-3a-carboxylic acid methyl ester
• 英文别名: Methyl 1-[2-(3,4-dimethoxyphenyl)ethyl]-6-(ethylthio)-1,2,3,4,5,7a-hexahydro-7a-hydroxy-2,5-dioxo-3aH-indole-3a-carboxylate；methyl 1-[2-(3,4-dimethoxyphenyl)ethyl]-6-ethylsulfanyl-7a-hydroxy-2,5-dioxo-3,4-dihydroindole-3a-carboxylate
• CAS: 202391-96-6
• 化学式: C₂₂H₂₇NO₇S
• 分子量: 449.525
• InChiKey: SVESEITYASXFEY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  31
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  128
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  methyl 4-[2-(3,4-dimethoxyphenyl)ethyl-[(E)-4-ethylsulfinyl-3-methoxybut-2-enoyl]amino]-2-methylidene-4-oxobutanoate 在 三氟化硼乙醚 、 三氟乙酸酐 作用下， 以 二氯甲烷 为溶剂， 以51%的产率得到1-[2-(3,4-Dimethoxy-phenyl)-ethyl]-6-ethylsulfanyl-7a-hydroxy-2,5-dioxo-1,2,3,4,5,7a-hexahydro-indole-3a-carboxylic acid methyl ester
  参考文献：
  名称：

  A Triple Cascade Sequence as a Strategy for the Construction of the Erythrinane Skeleton

  摘要：

  alpha-Thiocarbocations generated from Pummerer reactions of several o-imido sulfoxides were intercepted by adjacent carbonyl groups to produce alpha-amido-substituted isobenzofurans as transient intermediates. When an olefinic tether was present, intramolecular Diels-Alder cycloaddition occurred followed by a ring-opening-elimination sequence that produced an N-acyliminium ion. Deprotonation of the iminium ion led to oxindole derivatives in good yields, When the iminium ion contained both a Mocking substituent, such as a carbomethoxy group, as a ell as an activated aromatic pi-tether, the N-acyliminium ion intermediate underwent stereoselective spirocyclization to afford cis-3,4-benzoerythrinane or homoerythrinane derivatives in good yield. The overall triple cascade sequence represents an efficient one-pot approach toward the erythrina skeleton in which the spirocyclic ABC skeleton is assembled in a single operation. The scope and limitations of the triple cascade were explored by varying both the olefinic and nucleophilic tethers. The required sulfoxide precursors for these Pummerer-induced transformations were easily synthesized starting from 2-[(ethylthio)methyl]benzoic acid. The tandem Pummerer/Diels-Alder/N-acyliminium ion cyclization was used for the synthesis of indoloisoquinoline 38. Since compound 38 was converted to 47 which, in turn, was transformed into erysotramidine (2), its preparation represents an extraordinarily facile, formal synthesis of this member of the Erythrina alkaloid family.

  DOI：

  10.1021/jo9716183