Methanesulfonic acid 2-(1-benzyloxymethyl-3-indol-1-yl-propoxy)-ethyl ester | 336883-78-4

• 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: Methanesulfonic acid 2-(1-benzyloxymethyl-3-indol-1-yl-propoxy)-ethyl ester
• CAS: 336883-78-4
• 化学式: C₂₂H₂₇NO₅S
• 分子量: 417.526
• InChiKey: QFZOXIZVQOYULH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.61
• 重原子数：
  29.0
• 可旋转键数：
  12.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  66.76
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  Methanesulfonic acid 2-(1-benzyloxymethyl-3-indol-1-yl-propoxy)-ethyl ester 在 碘代三甲硅烷 、 sodium hydride 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.75h， 生成 18-(Hydroxymethyl)-17-oxa-4,14,21-triazahexacyclo[19.6.1.17,14.02,6.08,13.022,27]nonacosa-1(28),2(6),7(29),8,10,12,22,24,26-nonaene-3,5-dione
  参考文献：
  名称：

  Cyclization Strategies for the Synthesis of Macrocyclic Bisindolylmaleimides

  摘要：

  Three new approaches to the synthesis of macrocyclic bisindolylmaleimides 1-4 have been identified. Two strategies afford 8, the penultimate intermediate for the synthesis of 1-4, in 73% and 32% yield by intramolecular cyclization of 31 and 40, respectively. The optimum synthesis of 1 was achieved in nine steps and 15% yield by intramolecular formation of the macrocycle and maleimide in one step by reaction of the sodium indolate of 12 with methyl indole-3-glyoxylate 47. The mechanism of this reaction has been elucidated, using the trityl-protected derivative, to involve initial formation of the tricarbonyl im ide 48, followed by irreversible alkylation of the indole nitrogen to generate the 17-membered macrocycle 49. Cyclization of 49 to hydroxymaleimide 50 and subsequent dehydration afforded 8a. This approach eliminated the problem of dimerization observed in the intramolecular cyclization reactions.

  DOI：

  10.1021/jo001605g
• 作为产物：
  描述：

  6,7,10,11-tetrahydro-9-[(phenylmethoxy)methyl]-9H,18H-5,21:12,17-dimethenodibenzo[e,k]pyrrolo[3,4-h][1,4,13]oxadiazacyclohexadecine-18,20(19H)-dione 、 甲基磺酸酐 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 以95%的产率得到Methanesulfonic acid 2-(1-benzyloxymethyl-3-indol-1-yl-propoxy)-ethyl ester
  参考文献：
  名称：

  Cyclization Strategies for the Synthesis of Macrocyclic Bisindolylmaleimides

  摘要：

  Three new approaches to the synthesis of macrocyclic bisindolylmaleimides 1-4 have been identified. Two strategies afford 8, the penultimate intermediate for the synthesis of 1-4, in 73% and 32% yield by intramolecular cyclization of 31 and 40, respectively. The optimum synthesis of 1 was achieved in nine steps and 15% yield by intramolecular formation of the macrocycle and maleimide in one step by reaction of the sodium indolate of 12 with methyl indole-3-glyoxylate 47. The mechanism of this reaction has been elucidated, using the trityl-protected derivative, to involve initial formation of the tricarbonyl im ide 48, followed by irreversible alkylation of the indole nitrogen to generate the 17-membered macrocycle 49. Cyclization of 49 to hydroxymaleimide 50 and subsequent dehydration afforded 8a. This approach eliminated the problem of dimerization observed in the intramolecular cyclization reactions.

  DOI：

  10.1021/jo001605g