12,15,18-Trioxa-1,8,22,29,32,37-hexazatetracyclo[27.5.5.13,7.123,27]hentetraconta-3(41),4,6,23,25,27(40)-hexaene | 1039510-47-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 12,15,18-Trioxa-1,8,22,29,32,37-hexazatetracyclo[27.5.5.13,7.123,27]hentetraconta-3(41),4,6,23,25,27(40)-hexaene
• 英文别名: 12,15,18-trioxa-1,8,22,29,32,37-hexazatetracyclo[27.5.5.13,7.123,27]hentetraconta-3(41),4,6,23,25,27(40)-hexaene
• CAS: 1039510-47-8
• 化学式: C₃₂H₅₂N₆O₃
• 分子量: 568.803
• InChiKey: UZSDFZWFZRGOCD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  41
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  82.3
• 氢给体数：
  4
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  12,15,18-Trioxa-1,8,22,29,32,37-hexazatetracyclo[27.5.5.13,7.123,27]hentetraconta-3(41),4,6,23,25,27(40)-hexaene 在 potassium carbonate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 、 sodium t-butanolate 作用下， 以 1,4-二氧六环 、 乙腈 为溶剂， 反应 72.0h， 生成 12,15,18,43,46,49-hexaoxa-1,8,22,29,32,39,53,60-octaazaheptacyclo[30.30.2.2^29,60.13,7.1^23,27.1^34,38.1^54,58]heptaconta-3(70),4,6,23(69),24,26,34(68),35,37,54(67),55,57-dodecaene
  参考文献：
  名称：

  Pd-catalyzed amination in the synthesis of cyclen-based macrotricycles

  摘要：

  Three approaches to three types of cyclen-based macrotricycles have been elaborated starting from trans-bis(3-bromobenzyl)cyclen. The macrotricycles were synthesized via Pd-catalyzed amination. The first approach employed consecutive macrocyclization and benzylation steps giving a cage-like tricycle. In the second, cyclen amino groups were Boc-protected prior to formation of the second and the third rings. In the third method, macrotricycles were synthesized according to a one-step procedure using diazacrown ethers. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2011.11.024
• 作为产物：
  描述：

  1,7-di(3-bromobenzyl)cyclen 、 4,7,10-三氧-1,13-十三烷二胺 在 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 、 sodium t-butanolate 作用下， 以 1,4-二氧六环 为溶剂， 反应 0.03h， 以28%的产率得到12,15,18-Trioxa-1,8,22,29,32,37-hexazatetracyclo[27.5.5.13,7.123,27]hentetraconta-3(41),4,6,23,25,27(40)-hexaene
  参考文献：
  名称：

  Synthesis of Macrobi- and Macrotricyclic Compounds Comprising Pyrimidyl Substituted Cyclen and Cyclam

  摘要：

  The synthesis of novel N-1,N-7-bis(bromobenzyl)cyclens and N-1,N-8-bis(bromobenzyl)cyclens is described. Arylation of these compounds with excess 4,6-dichloropyrimidine and 2-chloropyrimidine gave corresponding tetrasubstituted cyclen and cyclam in good yields. Bis(bromobenzyl)bis(pyrimidyl) substituted cyclens and cyclams were used in the Pd-catalyzed reactions with polyamines to give macrobi- and macrotricycles. The yields of macropolycyclic compounds were shown to be dependent on the nature of starting tetraazamacrocycles and polyamines. In the case of cyclam monopyrimidyl derivatives were also obtained and macropolycyclic compounds were synthesized on their base.

  DOI：

  10.3987/com-10-s(e)98

文献信息

• Pd-catalyzed amination in the synthesis of cyclen-based macrotricycles
  作者：Sergei M. Kobelev、Alexei D. Averin、Alexei K. Buryak、Franck Denat、Roger Guilard、Irina P. Beletskaya

  DOI：10.1016/j.tetlet.2011.11.024

  日期：2012.1

  Three approaches to three types of cyclen-based macrotricycles have been elaborated starting from trans-bis(3-bromobenzyl)cyclen. The macrotricycles were synthesized via Pd-catalyzed amination. The first approach employed consecutive macrocyclization and benzylation steps giving a cage-like tricycle. In the second, cyclen amino groups were Boc-protected prior to formation of the second and the third rings. In the third method, macrotricycles were synthesized according to a one-step procedure using diazacrown ethers. (C) 2011 Elsevier Ltd. All rights reserved.
• Synthesis of Macrobi- and Macrotricyclic Compounds Comprising Pyrimidyl Substituted Cyclen and Cyclam
  作者：Irina P. Beletskaya、Roger Guilard、Sergei M. Kobelev、Alexei D. Averin、Alexei K. Buryak、Franck Denat

  DOI：10.3987/com-10-s(e)98

  日期：——

  The synthesis of novel N-1,N-7-bis(bromobenzyl)cyclens and N-1,N-8-bis(bromobenzyl)cyclens is described. Arylation of these compounds with excess 4,6-dichloropyrimidine and 2-chloropyrimidine gave corresponding tetrasubstituted cyclen and cyclam in good yields. Bis(bromobenzyl)bis(pyrimidyl) substituted cyclens and cyclams were used in the Pd-catalyzed reactions with polyamines to give macrobi- and macrotricycles. The yields of macropolycyclic compounds were shown to be dependent on the nature of starting tetraazamacrocycles and polyamines. In the case of cyclam monopyrimidyl derivatives were also obtained and macropolycyclic compounds were synthesized on their base.
• Synthesis of a new family of bi- and polycyclic compounds via Pd-catalyzed amination of 1,7-di(3-bromobenzyl)cyclen
  作者：Alexei D. Averin、Anton V. Shukhaev、Alexei K. Buryak、Franck Denat、Roger Guilard、Irina P. Beletskaya

  DOI：10.1016/j.tetlet.2008.04.045

  日期：2008.6

  New bicyclic cryptand type compounds are synthesized by reacting 1,7-di(3-bromobenzyl)cyclen with 1 equiv of linear polyamines under dilute conditions using Pd-catalyzed amination. Bis(cyclen) and tris(cyclen) compounds containing linear polyamine linkers between benzylated cyclens are obtained by a similar procedure using different reaction conditions. Cyclization of these species via intramolecular catalytic diamination led to tri- and tetracyclic polyaza compounds. (c) 2008 Elsevier Ltd. All rights reserved.
• Macrobicyclic and Macrotricyclic Derivatives of N,N’,N’’,N’’’-Tetrasubstituted Cyclen and Cyclam
  作者：Irina P. Beletskaya、Alexei D. Averin、Sergei M. Kobelev、Alexei K. Buryak、Andrei I. Vovk、Valerii P. Kukhar、Franck Denat、Roger Guilard

  DOI：10.3987/com-14-s(k)71

  日期：——

  N,N',N '',N'''-Tetrabenzyl derivatives of cyclen and cyclam possessing two bromine atoms in trans-positioned phenyl rings were introduced in the Pd-catalyzed amination reactions with oxadiamines and polyamines to provide a wide series of macrobicyclic compounds with tetrabenzyl substituted cyclen and cyclam central moieties in yields up to 31%. Macrocycles based on 1,7-dibenzylcyclen were modified with two 3-bromobenzyl substituents and introduced in the Pd-catalyzed macrocyclization with di- and trioxadiamines to afford spherically shaped macrotricyclic cryptands in yields up to 33%. An alternative approach to isomeric macrotricyclic cryptands employed Pd-catalyzed amination of di(Boc)-di(3-bromobenzyl)cyclen followed by the dialkylation of the resulting bicycle with two bromobenzyl groups and final catalytic macrocyclization step (yields up to 24%).