(11S)-10,13-Dioxo-2-oxa-11-methyl-9,12-diazatricyclo<14.2.2.1^3,7>heneicosa-3,5,7(21),16,18,19-hexaene

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酰胺类
• 英文名称: (11S)-10,13-Dioxo-2-oxa-11-methyl-9,12-diazatricyclo<14.2.2.1^3,7>heneicosa-3,5,7(21),16,18,19-hexaene
• 英文别名: (11S)-10,13-dioxo-11-methyl-2-oxa-9,12-diazatricyclo<14.2.2.1^3,7>heneicosa-3,5,7(21),16,18,19-hexaene；(11S)-11-methyl-2-oxa-9,12-diazatricyclo[14.2.2.13,7]henicosa-1(18),3,5,7(21),16,19-hexaene-10,13-dione
• 化学式: C₁₉H₂₀N₂O₃
• 分子量: 324.379
• InChiKey: QJKXYYRHFPRACC-ZDUSSCGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  24
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  67.4
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  4-氟-3-硝基苄醇 在 盐酸 、 亚硝酸特丁酯 、 水 、 三溴化磷 、 铁粉 、 sodium hydride 、 potassium carbonate 、 iron(II) sulfate 、 N,N-二甲基甲酰胺 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 反应 37.25h， 生成 (11S)-10,13-Dioxo-2-oxa-11-methyl-9,12-diazatricyclo<14.2.2.1^3,7>heneicosa-3,5,7(21),16,18,19-hexaene
  参考文献：
  名称：

  SNAr-Based Macrocyclization: An Application to the Synthesis of Vancomycin Family Models

  摘要：

  The first examples of macrocyclization using the intramolecular SNAr reaction are reported. The method has allowed the efficient preparation of the elusive 16-membered macrocyclic COD and DOE rings related to vancomycin. The mild conditions used allow the incorporation of very racemization-prone amino acids, such as p-methoxyphenylglycine, into the peptide chain. After serving as an activator, the nitro group ortho to the diaryl ether linkage is converted either into a chlorine or a hydrogen atom, thus achieving the substitution pattern found in the vancomycin family of glycopeptides. When compound 20 was submitted to the same macrocyclization conditions, two atropisomers 21 and 22 were isolated and characterized.

  DOI：

  10.1021/jo00098a010

文献信息

• Vancomycin and ristocetin models: synthesis via the Ullmann macrocyclization reaction
  作者：Dale L. Boger、Yuji Nomoto、Bradley R. Teegarden

  DOI：10.1021/jo00058a024

  日期：1993.3

  The preparations of 2 and 3, the parent skeletons of the CD and DE diphenyl ether 16-membered ring systems of vancomycin and ristocetin, based on the implementation of an intramolecular Ullmann macrocyclization reaction are detailed. Additional studies which define the scope of substrates suitable for use in the Ullmann macrocyclization reaction are described including a limited study of those bearing centers capable of racemization. Within the limited series of agents examined, Ullmann macrocyclization closure of the DE ring system was found to occur at a faster rate and in higher overall yields than those providing the CD ring system. N-Methylation of the amide linking chain decelerates or inhibits Ullmann macrocyclization and a-substitution of the central amino acid of the linking chain significantly increases the cyclization conversions. Racemization of the central amino acid of the linking amide chain was found to be minimal (5%) under reaction conditions where the secondary amides are deliberately deprotonated prior to exposure of the substrate to the thermal, basic reaction conditions.
• SNAr-Based Macrocyclization: An Application to the Synthesis of Vancomycin Family Models
  作者：Rene Beugelmans、Girij Pal Singh、Michele Bois-Choussy、Jacqueline Chastanet、Jieping Zhu

  DOI：10.1021/jo00098a010

  日期：1994.9

  The first examples of macrocyclization using the intramolecular SNAr reaction are reported. The method has allowed the efficient preparation of the elusive 16-membered macrocyclic COD and DOE rings related to vancomycin. The mild conditions used allow the incorporation of very racemization-prone amino acids, such as p-methoxyphenylglycine, into the peptide chain. After serving as an activator, the nitro group ortho to the diaryl ether linkage is converted either into a chlorine or a hydrogen atom, thus achieving the substitution pattern found in the vancomycin family of glycopeptides. When compound 20 was submitted to the same macrocyclization conditions, two atropisomers 21 and 22 were isolated and characterized.