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Flexible Synthesis of Rigid Cyclophanes - Synthesis and derivatisation of 2,7-diaza-1,2,3,6,7,8-hexahydropyrene into chiral macrocycles

Toftered, Jörgen LU (2004)
Abstract
Rigid, chiral and amphiphilic cyclophanes of potential use as biomimetic host molecules were prepared by cyclic dimerisation of chiral diamino building blocks with amino-reactive cross-linking reagents. A reliable synthesis of the scaffold 2,7-diaza-1,2,3,6,7,8-hexahydropyrene was developed. Chiral bidentate building blocks were formed by acylation of the aromatic diamine 2,7-diaza-1,2,3,6,7,8-hexahydropyrene with L-amino acids. 1,5-Difluoro-2,4-dinitrobenzene was employed as a cross-linking reagent, stepwise nucleophilic aromatic substitution with bidentate building block gave rise to a range of macrocyclic bis-dinitrodianilines. Macrocyclic bis-ureas were formed by using substituted phenyl chloroformates as cross-linking reagents. The... (More)
Rigid, chiral and amphiphilic cyclophanes of potential use as biomimetic host molecules were prepared by cyclic dimerisation of chiral diamino building blocks with amino-reactive cross-linking reagents. A reliable synthesis of the scaffold 2,7-diaza-1,2,3,6,7,8-hexahydropyrene was developed. Chiral bidentate building blocks were formed by acylation of the aromatic diamine 2,7-diaza-1,2,3,6,7,8-hexahydropyrene with L-amino acids. 1,5-Difluoro-2,4-dinitrobenzene was employed as a cross-linking reagent, stepwise nucleophilic aromatic substitution with bidentate building block gave rise to a range of macrocyclic bis-dinitrodianilines. Macrocyclic bis-ureas were formed by using substituted phenyl chloroformates as cross-linking reagents. The substitution pattern of the phenyl chloroformates was optimised the synthesis of macrocycles. This investigation favoured phenyl chloroformates substituted with electron-withdrawing groups of intermediate power. Applying the results from the investigation of phenyl chloroformate substituents, macrocyclic bis-thioureas were prepared by using substituted phenyl chlorothionoformates as cross-linking reagents. The synthesis of chiral macrocycles was further diversified by incorporating other aromatic diamines as scaffolds, namely p-xylylenediamine and bis-2,3:6,7-iminodimethylene-anthracene. Future development and application of the macrocycles was discussed with emphasis on rational design based on conformational analyses. (Less)
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author
opponent
  • Almqvist, Fredrik, PhD, Umeå University
organization
publishing date
type
Thesis
publication status
published
subject
keywords
Macromolecular chemistry, Makromolekylär kemi, biomimetic, cross-linking, thiourea, urea, difluorodinitrobenzene, cyclodimerisation, Cyclophanes, macrocycles
pages
84 pages
publisher
Bioorganic Chemistry, Lund University
defense location
, Kemicentrum sal K:C, Lunds Tekniska Högskola
defense date
2004-12-10 13:30
ISBN
91-628-6341-X
language
English
LU publication?
yes
id
5be37a95-ed80-4141-ad5b-19840f8ce6fc (old id 467665)
date added to LUP
2007-10-13 15:14:35
date last changed
2016-09-19 08:45:14
@phdthesis{5be37a95-ed80-4141-ad5b-19840f8ce6fc,
  abstract     = {Rigid, chiral and amphiphilic cyclophanes of potential use as biomimetic host molecules were prepared by cyclic dimerisation of chiral diamino building blocks with amino-reactive cross-linking reagents. A reliable synthesis of the scaffold 2,7-diaza-1,2,3,6,7,8-hexahydropyrene was developed. Chiral bidentate building blocks were formed by acylation of the aromatic diamine 2,7-diaza-1,2,3,6,7,8-hexahydropyrene with L-amino acids. 1,5-Difluoro-2,4-dinitrobenzene was employed as a cross-linking reagent, stepwise nucleophilic aromatic substitution with bidentate building block gave rise to a range of macrocyclic bis-dinitrodianilines. Macrocyclic bis-ureas were formed by using substituted phenyl chloroformates as cross-linking reagents. The substitution pattern of the phenyl chloroformates was optimised the synthesis of macrocycles. This investigation favoured phenyl chloroformates substituted with electron-withdrawing groups of intermediate power. Applying the results from the investigation of phenyl chloroformate substituents, macrocyclic bis-thioureas were prepared by using substituted phenyl chlorothionoformates as cross-linking reagents. The synthesis of chiral macrocycles was further diversified by incorporating other aromatic diamines as scaffolds, namely p-xylylenediamine and bis-2,3:6,7-iminodimethylene-anthracene. Future development and application of the macrocycles was discussed with emphasis on rational design based on conformational analyses.},
  author       = {Toftered, Jörgen},
  isbn         = {91-628-6341-X},
  keyword      = {Macromolecular chemistry,Makromolekylär kemi,biomimetic,cross-linking,thiourea,urea,difluorodinitrobenzene,cyclodimerisation,Cyclophanes,macrocycles},
  language     = {eng},
  pages        = {84},
  publisher    = {Bioorganic Chemistry, Lund University},
  school       = {Lund University},
  title        = {Flexible Synthesis of Rigid Cyclophanes - Synthesis and derivatisation of 2,7-diaza-1,2,3,6,7,8-hexahydropyrene into chiral macrocycles},
  year         = {2004},
}