di-tert-butyl 12,15,18-trioxa-1,8,22,29,32,37-hexaazatetracyclo[27.5.5.1^3,7.1^23,27]hentetraconta-3(41),4,6,23(40),24,26-hexaene-32,37-dicarboxylate | 1352942-40-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: di-tert-butyl 12,15,18-trioxa-1,8,22,29,32,37-hexaazatetracyclo[27.5.5.1^3,7.1^23,27]hentetraconta-3(41),4,6,23(40),24,26-hexaene-32,37-dicarboxylate
• 英文别名: Ditert-butyl 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-32,37-dicarboxylate
• CAS: 1352942-40-5
• 化学式: C₄₂H₆₈N₆O₇
• 分子量: 769.038
• InChiKey: JCWFLQQLFRJJGI-UHFFFAOYSA-N

物化性质

• 沸点：
  845.3±65.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  55
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  117
• 氢给体数：
  2
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  di-tert-butyl 12,15,18-trioxa-1,8,22,29,32,37-hexaazatetracyclo[27.5.5.1^3,7.1^23,27]hentetraconta-3(41),4,6,23(40),24,26-hexaene-32,37-dicarboxylate 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 、 二氯甲烷 、 乙腈 为溶剂， 反应 24.0h， 生成 di-tert-butyl 11,14,17,50,53,56-hexaoxa-1,7,21,27,34,37,40,63-octaazaheptacyclo[25.19.13.5^34,40.2^3,6.2^22,25.1^28,32.1^42,46]heptaconta-3,5,22,24,28(66),29,31,42(60),43,45,67,69-dodecaene-37,63-dicarboxylate
  参考文献：
  名称：

  Macrobicyclic and Macrotricyclic Derivatives of N,N’,N’’,N’’’-Tetrasubstituted Cyclen and Cyclam

  摘要：

  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%).

  DOI：

  10.3987/com-14-s(k)71
• 作为产物：
  描述：

  二碳酸二叔丁酯 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 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 di-tert-butyl 12,15,18-trioxa-1,8,22,29,32,37-hexaazatetracyclo[27.5.5.1^3,7.1^23,27]hentetraconta-3(41),4,6,23(40),24,26-hexaene-32,37-dicarboxylate
  参考文献：
  名称：

  Macrobicyclic and Macrotricyclic Derivatives of N,N’,N’’,N’’’-Tetrasubstituted Cyclen and Cyclam

  摘要：

  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%).

  DOI：

  10.3987/com-14-s(k)71

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.