(2R,3S,11R,12S)-3,11-diphenoxy-19,22-dioxa-5,9-diazapentacyclo[21.4.0.02,5.09,12.013,18]heptacosa-1(27),13,15,17,23,25-hexaene-4,10-dione | 916145-01-2

• 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: (2R,3S,11R,12S)-3,11-diphenoxy-19,22-dioxa-5,9-diazapentacyclo[21.4.0.02,5.09,12.013,18]heptacosa-1(27),13,15,17,23,25-hexaene-4,10-dione
• CAS: 916145-01-2
• 化学式: C₃₅H₃₂N₂O₆
• 分子量: 576.649
• InChiKey: AUCMCYAIZSQPKF-NJRHJFJMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  43
• 可旋转键数：
  4
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  77.5
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2R,3S,11R,12S)-3,11-diphenoxy-19,22-dioxa-5,9-diazapentacyclo[21.4.0.02,5.09,12.013,18]heptacosa-1(27),13,15,17,23,25-hexaene-4,10-dione 在 lithium aluminium tetrahydride 、 三氯化铝 作用下， 以 四氢呋喃 为溶剂， 反应 0.33h， 以95%的产率得到(2S,3S,11R,12R)-3,11-diphenoxy-19,22-dioxa-5,9-diazapentacyclo[21.4.0.02,5.09,12.013,18]heptacosa-1(27),13,15,17,23,25-hexaene
  参考文献：
  名称：

  Synthesis of Highly Functionalized Macrocycles by the Peripheral Functionalization of Macrocyclic Diimines

  摘要：

  The easily available macrocyclic diimines 4-7 can be stereoselectively transformed to macrocyclic bis-beta-amino acids 13-17, macrocyclic bisazetidines 18-20, and macrocyclic bisamides 21 and 22 by means of the corresponding bis-beta-lactam scaffolds 8-12. These key intermediates are available through standard Staudinger reaction and obtained as the cis-cis diastereomers, exclusively. An interesting relation between the proximity of the reactive C=N bonds and the selectivity in the formation of the bis-beta-lactams 8-12 is observed. Thus, diimine 4 leads to low selectivities, producing a 1:1 mixture of cis-syn-cis and cis-anti-cis diastereomers, while diimines 5-7 having the diimine sites more separated lead almost exclusively to the cis-anti-cis diastereomers. The stereochemistry of all the products was unambiguously assigned by X-ray diffraction analysis of compounds cis-syn-cis 8 and cis-anti-cis 12-Co2CO6 complex.

  DOI：

  10.1021/jo0614689
• 作为产物：
  描述：

  (5Z,10Z)-8,9,17,18-Tetrahydro-7H-16,19-dioxa-6,10-diaza-dibenzo[a,g]cyclopentadecene 、 苯氧乙酰氯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 16.5h， 以27%的产率得到
  参考文献：
  名称：

  Synthesis of Highly Functionalized Macrocycles by the Peripheral Functionalization of Macrocyclic Diimines

  摘要：

  The easily available macrocyclic diimines 4-7 can be stereoselectively transformed to macrocyclic bis-beta-amino acids 13-17, macrocyclic bisazetidines 18-20, and macrocyclic bisamides 21 and 22 by means of the corresponding bis-beta-lactam scaffolds 8-12. These key intermediates are available through standard Staudinger reaction and obtained as the cis-cis diastereomers, exclusively. An interesting relation between the proximity of the reactive C=N bonds and the selectivity in the formation of the bis-beta-lactams 8-12 is observed. Thus, diimine 4 leads to low selectivities, producing a 1:1 mixture of cis-syn-cis and cis-anti-cis diastereomers, while diimines 5-7 having the diimine sites more separated lead almost exclusively to the cis-anti-cis diastereomers. The stereochemistry of all the products was unambiguously assigned by X-ray diffraction analysis of compounds cis-syn-cis 8 and cis-anti-cis 12-Co2CO6 complex.

  DOI：

  10.1021/jo0614689

文献信息

• Synthesis of Highly Functionalized Macrocycles by the Peripheral Functionalization of Macrocyclic Diimines
  作者：Miguel A. Sierra、Daniel Pellico、Mar Gómez-Gallego、María José Mancheño、Rosario Torres

  DOI：10.1021/jo0614689

  日期：2006.11.1

  The easily available macrocyclic diimines 4-7 can be stereoselectively transformed to macrocyclic bis-beta-amino acids 13-17, macrocyclic bisazetidines 18-20, and macrocyclic bisamides 21 and 22 by means of the corresponding bis-beta-lactam scaffolds 8-12. These key intermediates are available through standard Staudinger reaction and obtained as the cis-cis diastereomers, exclusively. An interesting relation between the proximity of the reactive C=N bonds and the selectivity in the formation of the bis-beta-lactams 8-12 is observed. Thus, diimine 4 leads to low selectivities, producing a 1:1 mixture of cis-syn-cis and cis-anti-cis diastereomers, while diimines 5-7 having the diimine sites more separated lead almost exclusively to the cis-anti-cis diastereomers. The stereochemistry of all the products was unambiguously assigned by X-ray diffraction analysis of compounds cis-syn-cis 8 and cis-anti-cis 12-Co2CO6 complex.