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Synthesis and applications of analogues of Tröger's base as molecular tubes, receptor and ligands

Hansson, Anna LU (2003)
Abstract
Tröger’s base was synthesized for the first time in 1887. The molecule is rigid, C2-symmetric and has a 90° angle, forming a chiral hydrophobic pocket. In this thesis, the synthesis of new analogues of Tröger’s base is described. 2- and 3-halo-substituted anilines have for the first time been condensed to Tröger’s base analogues. It has also been shown that anilines without substituents in para-position are capable of forming Tröger’s base analogues in one step. Since halogenated compounds are easy to modify, this means that it is now possible to synthesize many analogues not attainable earlier. The next part of the thesis describes the synthesis of a Tröger’s base analogue that might be capable of self-aggregating into a tube since it has... (More)
Tröger’s base was synthesized for the first time in 1887. The molecule is rigid, C2-symmetric and has a 90° angle, forming a chiral hydrophobic pocket. In this thesis, the synthesis of new analogues of Tröger’s base is described. 2- and 3-halo-substituted anilines have for the first time been condensed to Tröger’s base analogues. It has also been shown that anilines without substituents in para-position are capable of forming Tröger’s base analogues in one step. Since halogenated compounds are easy to modify, this means that it is now possible to synthesize many analogues not attainable earlier. The next part of the thesis describes the synthesis of a Tröger’s base analogue that might be capable of self-aggregating into a tube since it has a complementary hydrogen-bond-pattern in both ends. The first turn of a covalent tube has been synthesized using halogenated Tröger's base analogues as starting materials. Through step-wise build-up of the tube, we will have full control of the length of the tube. The tube will be soluble in both hydrophobic solvents and in acidic water-phase. A bis-crown ether analogue of Tröger’s base has been used as a receptor, discriminating between bis-ammonium salts of different lengths by determination of the association constants. The size of the hydrophobic pocket has been investigated by complexation with bis-ammonium salts carrying side-groups of different size. Finally, some analogues of Tröger’s base were synthesized and two of these were investigated as optically active ligands in two asymmetric reactions and managed to induce optical activity in a small degree in the products. (Less)
Abstract (Swedish)
Popular Abstract in Swedish

Trögers bas är en molekyl som syntetiserades första gången 1887. Molekylen är stel, C2-symmetrisk och böjd i ca 90° vinkel och den formar en kiral hydrofob ficka. I denna avhandling beskrivs syntesen av nya analoger av Trögers bas. Aniliner, substituerade med halider i 2- och 3-position, har för första gången kondenserats till analoger av Trögers bas. Dessutom har det visats att aniliner utan substituenter i position 4 kan forma analoger av Trögers bas i ett steg. Eftersom halogenerade föreningar är lätta att modifiera betyder detta att det nu är möjligt att syntetisera många analoger som det inte var möjligt att göra tidigare. Nästa del i avhandlingen beskriver syntesen av en analog av Trögers... (More)
Popular Abstract in Swedish

Trögers bas är en molekyl som syntetiserades första gången 1887. Molekylen är stel, C2-symmetrisk och böjd i ca 90° vinkel och den formar en kiral hydrofob ficka. I denna avhandling beskrivs syntesen av nya analoger av Trögers bas. Aniliner, substituerade med halider i 2- och 3-position, har för första gången kondenserats till analoger av Trögers bas. Dessutom har det visats att aniliner utan substituenter i position 4 kan forma analoger av Trögers bas i ett steg. Eftersom halogenerade föreningar är lätta att modifiera betyder detta att det nu är möjligt att syntetisera många analoger som det inte var möjligt att göra tidigare. Nästa del i avhandlingen beskriver syntesen av en analog av Trögers bas som har möjlighet att självaggregera till en tub eftersom den har ett komplementärt vätebindningsmönster i ändarna. Ett första varv av en kovalent tub har syntetiserats från en dihalogenerad Trögers bas. Genom att bygga upp tuben stegvis har man hela tiden kontroll över längden på tuben. Tuben kommer att ha fördelen av att vara löslig både i hydrofoba lösningsmedel och i sur vattenfas. En bis-kroneteranalog av Trögers bas har använts som en receptor och har påvisats kunna diskriminera mellan bis-ammoniumsalter av olika längder genom att bindningskonstanter bestämts. Storleken av den hydrofoba fickan har undersökts genom att binda in bis-ammoniumsalter med olika stora sidogrupper. Slutligen syntetiserades några analoger av Trögers bas varav två testades som optiskt aktiva ligander i två olika asymmetriska reaktioner. (Less)
Please use this url to cite or link to this publication:
author
supervisor
opponent
  • Prof. Siegel, Jay S.
organization
publishing date
type
Thesis
publication status
published
subject
keywords
Organisk kemi, Organic chemistry, bis-crown ether analogue, molecular recognition, molecular tubes, Tröger's base, dihalo-analogues
pages
86 pages
publisher
Organic Chemistry, Lund University
defense location
Chemical Center, Hall B
defense date
2003-09-18 10:30:00
ISBN
91-628-5713-4
language
English
LU publication?
yes
additional info
Article: I.Synthesis of Dihalosubstituted Analogues of Tröger’s Base from ortho- and meta-Substituted AnilinesAnna Hansson, Jacob Jensen, Ola F. Wendt and Kenneth WärnmarkEuropean Journal of Organic Chemistry 2003, 3179–3188 Article: II.Synthesis of an Analogue of Tröger’s Base, 8H,16H-7,15-methano-di(2H-isoquinolin-3-ono)-[6,5-b:6',5'-f][1,5]diazocine, towards chirality induced self-assemblyAnna Hansson, Per-Ola Norrby, Ola F. Wendt and Kenneth Wärnmarkin manuscript Article: III.A Bis(Crown-Ether) Analogue of Tröger’s Base: Recognition of Achiral and Chiral Primary Bisammonium SaltsAnna Hansson, Per-Ola Norrby and Kenneth WärnmarkTetrahedron Letters 1998, 39, 4565–4568 Article: IV.Exploring the solvophobic binding pocket of Tröger's Base. Selectivity in the recognition of 4-subststituted heptane-1,7-diyl bisammonium saltsJacob Jensen, Anna Hansson, Per-Ola Norrby, Sami Dawaigher and Kenneth Wärnmarkin 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
758c317d-e5f1-44ba-aba6-fbfc966084e5 (old id 466046)
date added to LUP
2016-04-04 10:20:05
date last changed
2018-11-21 20:58:09
@phdthesis{758c317d-e5f1-44ba-aba6-fbfc966084e5,
  abstract     = {Tröger’s base was synthesized for the first time in 1887. The molecule is rigid, C2-symmetric and has a 90° angle, forming a chiral hydrophobic pocket. In this thesis, the synthesis of new analogues of Tröger’s base is described. 2- and 3-halo-substituted anilines have for the first time been condensed to Tröger’s base analogues. It has also been shown that anilines without substituents in para-position are capable of forming Tröger’s base analogues in one step. Since halogenated compounds are easy to modify, this means that it is now possible to synthesize many analogues not attainable earlier. The next part of the thesis describes the synthesis of a Tröger’s base analogue that might be capable of self-aggregating into a tube since it has a complementary hydrogen-bond-pattern in both ends. The first turn of a covalent tube has been synthesized using halogenated Tröger's base analogues as starting materials. Through step-wise build-up of the tube, we will have full control of the length of the tube. The tube will be soluble in both hydrophobic solvents and in acidic water-phase. A bis-crown ether analogue of Tröger’s base has been used as a receptor, discriminating between bis-ammonium salts of different lengths by determination of the association constants. The size of the hydrophobic pocket has been investigated by complexation with bis-ammonium salts carrying side-groups of different size. Finally, some analogues of Tröger’s base were synthesized and two of these were investigated as optically active ligands in two asymmetric reactions and managed to induce optical activity in a small degree in the products.},
  author       = {Hansson, Anna},
  isbn         = {91-628-5713-4},
  language     = {eng},
  publisher    = {Organic Chemistry, Lund University},
  school       = {Lund University},
  title        = {Synthesis and applications of analogues of Tröger's base as molecular tubes, receptor and ligands},
  year         = {2003},
}