(9S,10R)-9,10-Diphenyl-1,4,8,11-tetraaza-cyclotetradecane-5,14-dione

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (9S,10R)-9,10-Diphenyl-1,4,8,11-tetraaza-cyclotetradecane-5,14-dione
• 英文别名: (9R,10S)-9,10-diphenyl-1,4,8,11-tetrazacyclotetradecane-5,14-dione
• 化学式: C₂₂H₂₈N₄O₂
• 分子量: 380.49
• InChiKey: DVWAMEKIEUNDJE-SZPZYZBQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  28
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  82.3
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  3-{[1-Phenyl-meth-(E)-ylidene]-amino}-N-[2-(3-{[1-phenyl-meth-(E)-ylidene]-amino}-propionylamino)-ethyl]-propionamide 在 甲烷磺酸 、 锌 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 (9S,10R)-9,10-Diphenyl-1,4,8,11-tetraaza-cyclotetradecane-5,14-dione 、 (9R,10R)-9,10-Diphenyl-1,4,8,11-tetraaza-cyclotetradecane-5,14-dione
  参考文献：
  名称：

  Synthesis of Nitrogen-Containing Macrocycles with Reductive Intramolecular Coupling of Aromatic Diimines

  摘要：

  Reductive intramolecular coupling of aromatic diimines is an effective method for the synthesis of a variety of nitrogen-containing macrocycles. 1,4-Diazacrown ethers 3 were effectively synthesized by intramolecular coupling of bis(imino ethers) 9 promoted by electroreduction (method A) or chemical reduction with zinc powder (method B) in the presence of methanesulfonic acid. In spite of the formation of macrocycles, the yields of 3 were relatively high. This can be explained by the formation of proton-bridged intermediates 14, in which intramolecular hydrogen bonds are formed between hydrogen and oxygen atoms of diiminium salts. Method B was more effective in the formation of 1,4-diaza-12-crown-4 derivatives 3 (n = 1) due to the template effect of Zn2+. Optically active macrocyclic bislactones 4 were synthesized stereoselectively by reductive intramolecular coupling of bis(imino esters) 20 with zinc powder (method B). The high stereoselectivity is explained by considering proton-bridged intermediate 23. The resultant compounds 4 were transformed to optically active 1,2-diarylethylenediamines 7. Various sizes of macrocyclic bislactams 5 were synthesized by reductive intramolecular coupling of bis(imino amides) 26 with zinc powder (method B). Reduction of 5 gave the corresponding macrocyclic polyamines 6.

  DOI：

  10.1021/jo00118a013

文献信息

• Synthesis of Nitrogen-Containing Macrocycles with Reductive Intramolecular Coupling of Aromatic Diimines
  作者：Naoki Kise、Hideaki Oike、Eiichi Okazaki、Masami Yoshimoto、Tatsuya Shono

  DOI：10.1021/jo00118a013

  日期：1995.6

  Reductive intramolecular coupling of aromatic diimines is an effective method for the synthesis of a variety of nitrogen-containing macrocycles. 1,4-Diazacrown ethers 3 were effectively synthesized by intramolecular coupling of bis(imino ethers) 9 promoted by electroreduction (method A) or chemical reduction with zinc powder (method B) in the presence of methanesulfonic acid. In spite of the formation of macrocycles, the yields of 3 were relatively high. This can be explained by the formation of proton-bridged intermediates 14, in which intramolecular hydrogen bonds are formed between hydrogen and oxygen atoms of diiminium salts. Method B was more effective in the formation of 1,4-diaza-12-crown-4 derivatives 3 (n = 1) due to the template effect of Zn2+. Optically active macrocyclic bislactones 4 were synthesized stereoselectively by reductive intramolecular coupling of bis(imino esters) 20 with zinc powder (method B). The high stereoselectivity is explained by considering proton-bridged intermediate 23. The resultant compounds 4 were transformed to optically active 1,2-diarylethylenediamines 7. Various sizes of macrocyclic bislactams 5 were synthesized by reductive intramolecular coupling of bis(imino amides) 26 with zinc powder (method B). Reduction of 5 gave the corresponding macrocyclic polyamines 6.