Flexible Synthesis of Rigid Cyclophanes - Synthesis and derivatisation of 2,7-diaza-1,2,3,6,7,8-hexahydropyrene into chiral macrocycles
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/467665
- author
- Toftered, Jörgen LU
- supervisor
- opponent
-
- Almqvist, Fredrik, PhD, Umeå University
- organization
- publishing date
- 2004
- 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 13:30:00
- ISBN
- 91-628-6341-X
- language
- English
- LU publication?
- yes
- additional info
- Article: S. Bhattacharyya, J. Toftered and U.J. Nilsson;Synthesis of Rigid Polycyclic Secondary Diamines: Bis-(2,3:6,7-Iminodimethylene)anthracene and Bis-(2,3:6,7-Iminodimethylene)-9,10-dicarboxyethenoanthracene.,SYNLETT, 2003, 1361-1363. Article: J. Toftered and U.J. Nilsson;Synthesis of Chiral Macrocycles by Cyclodimerization of Diamines with Stepwise Nucleophilic Aromatic Substitution of 1,5-Difluoro-2,4-dinitrobenzene.,SYNLETT, 2004, 2517-2520. Article: J. Toftered and U.J. Nilsson;Reactivity fine-tuning of phenyl carbamates for efficient synthesis of amphiphilic macrocyclic bis-ureas and bis-thioureas.In manuscript. Article: J. Toftered and U.J. Nilsson;Synthesis of chiral macrocycles incorporating two different aromatic diamines.In manuscript. The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Organic chemistry (S/LTH) (011001240)
- id
- 5be37a95-ed80-4141-ad5b-19840f8ce6fc (old id 467665)
- date added to LUP
- 2016-04-04 12:12:38
- date last changed
- 2018-11-21 21:09:38
@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}},
keywords = {{Macromolecular chemistry; Makromolekylär kemi; biomimetic; cross-linking; thiourea; urea; difluorodinitrobenzene; cyclodimerisation; Cyclophanes; macrocycles}},
language = {{eng}},
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}},
url = {{https://lup.lub.lu.se/search/files/5953205/1472238.pdf}},
year = {{2004}},
}