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Improving Tröger's Base Chemistry : Developing the Chemistry of Tröger's base

Dawaigher, Sami LU (2018)
Abstract
The Tröger’s base framework has been implemented in two different receptors. The first of these receptors, incorporating two 18-crown-6 moities, was used as a host in a binding study together with a sieries of bisammonium salts that yielded different binding constants that were then used as a benchmark to compare different computational methods (Molecular Mechanics (MM) and Density Functional Theory (DFT)) in predicting the correct results where the MM methods proved more effective. The second of the receptors incorporated two Tröger’s base moieties linked together with two crown ether straps. This receptor was tested for it’s affinity towards different metal cations, the receptor proved too hindered to accomodate any cations except Fe3+.... (More)
The Tröger’s base framework has been implemented in two different receptors. The first of these receptors, incorporating two 18-crown-6 moities, was used as a host in a binding study together with a sieries of bisammonium salts that yielded different binding constants that were then used as a benchmark to compare different computational methods (Molecular Mechanics (MM) and Density Functional Theory (DFT)) in predicting the correct results where the MM methods proved more effective. The second of the receptors incorporated two Tröger’s base moieties linked together with two crown ether straps. This receptor was tested for it’s affinity towards different metal cations, the receptor proved too hindered to accomodate any cations except Fe3+. Furthermore, the reactivity of Tröger’s base with lithium amide bases has been investigated extensively. A new protocol for preparing mono- and bissubstistuted Tröger’s base derivatives has been developed where Tröger’s base is treated with sBuLi/TMEDA followed by an electrophilic quench resulting in a Tröger’s base derivative substituted in the exo-6 and exo-12 positions. In addition to this method, a method for converting exo-6- and exo-12 substituted Tröger’s base amides into endo-6 and endo-12 substituted Tröger’s base amide has been developed. A study of the reduction of Tröger’s base amides is described herein. (Less)
Abstract (Swedish)
The Tröger’s base framework has been implemented in two different receptors. The first of these receptors,
incorporating two 18-crown-6 moities, was used as a host in a binding study together with a sieries of bisammonium salts that yielded different binding constants that were then used as a benchmark to compare different computational methods (Molecular Mechanics (MM) and Density Functional Theory (DFT)) in predicting the correct results where the MM methods proved more effective. The second of the receptors incorporated two Tröger’s base moieties linked together with two crown ether straps. This receptor was tested for it’s affinity towards different metal cations, the receptor proved too hindered to accomodate any cations except... (More)
The Tröger’s base framework has been implemented in two different receptors. The first of these receptors,
incorporating two 18-crown-6 moities, was used as a host in a binding study together with a sieries of bisammonium salts that yielded different binding constants that were then used as a benchmark to compare different computational methods (Molecular Mechanics (MM) and Density Functional Theory (DFT)) in predicting the correct results where the MM methods proved more effective. The second of the receptors incorporated two Tröger’s base moieties linked together with two crown ether straps. This receptor was tested for it’s affinity towards different metal cations, the receptor proved too hindered to accomodate any cations except Fe3+. Furthermore, the reactivity of Tröger’s base with lithium amide bases has been investigated extensively. A new protocol for preparing mono- and bissubstistuted Tröger’s base derivatives has been developed where Tröger’s base is treated with sBuLi/TMEDA followed by an electrophilic quench resulting in a Tröger’s base derivative substituted in the exo-6 and exo-12 positions. In addition to this method, a method for converting exo-6- and exo-12 substituted Tröger’s base amides into endo-6 and endo-12 substituted Tröger’s base amide has been developed. A study of the reduction of Tröger’s base amides is described herein. (Less)
Please use this url to cite or link to this publication:
author
supervisor
opponent
  • Professor Brønsted Nielsen, Mogens, Köpenhamns universitet
organization
publishing date
type
Thesis
publication status
published
subject
keywords
Tröger’s base, Host Guest Chemistry, Metalation, Computational Chemistry, Supramolecular Chemistry
pages
118 pages
publisher
Lunds universitet
defense location
Sal C, Kemicentrum, Naturvetarvägen 14, Lund
defense date
2018-12-20 10:15:00
ISBN
978-91-7422-615-7
978-91-7422-614-0
language
English
LU publication?
yes
id
7a391d9a-af8d-41e4-8534-d6a17b23d854
date added to LUP
2018-11-26 09:10:50
date last changed
2018-11-27 10:49:50
@phdthesis{7a391d9a-af8d-41e4-8534-d6a17b23d854,
  abstract     = {The Tröger’s base framework has been implemented in two different receptors. The first of these receptors, incorporating two 18-crown-6 moities, was used as a host in a binding study together with a sieries of bisammonium salts that yielded different binding constants that were then used as a benchmark to compare different computational methods (Molecular Mechanics (MM) and Density Functional Theory (DFT)) in predicting the correct results where the MM methods proved more effective. The second of the receptors incorporated two Tröger’s base moieties linked together with two crown ether straps. This receptor was tested for it’s affinity towards different metal cations, the receptor proved too hindered to accomodate any cations except Fe3+. Furthermore, the reactivity of Tröger’s base with lithium amide bases has been investigated extensively. A new protocol for preparing mono- and bissubstistuted Tröger’s base derivatives has been developed where Tröger’s base is treated with sBuLi/TMEDA followed by an electrophilic quench resulting in a Tröger’s base derivative substituted in the exo-6 and exo-12 positions. In addition to this method, a method for converting exo-6- and exo-12 substituted Tröger’s base amides into endo-6 and endo-12 substituted Tröger’s base amide has been developed. A study of the reduction of Tröger’s base amides is described herein.},
  author       = {Dawaigher, Sami},
  isbn         = {978-91-7422-615-7 },
  language     = {eng},
  publisher    = {Lunds universitet},
  school       = {Lund University},
  title        = {Improving Tröger's Base Chemistry : Developing the Chemistry of Tröger's base},
  url          = {https://lup.lub.lu.se/search/ws/files/54869012/Spikfil_Sami_D.pdf},
  year         = {2018},
}