Enhancing the cooperative binding properties of1,1'-bis(1,2,3,4-tetrahydroisoquinolines)
type: CreativeWork
description: The design of partially reduced 1,1'-bisisoquinoline derivatives was investigated with the aim of controlling the conformation about the C1-C1' axis. This would produce ligands with unusual but predictable ligand binding properties, particularly cooperativity. The introduction of ω-aminoalkyl, ω-azidoalkyl, ω-alkynyl and ω-alkenyl groups onto the nitrogens of the reduced bisisoquinoline core was conducted with the intention of broadening the scope of the ligand. Subsequent epoxidation, hydroboration and Huisgen 1,3-dipolar cycloaddition of terminal unsaturated groups and nucleophilic displacement of the chlorine of the corresponding known bischloroacetyl derivative afforded representative examples of new ligand types for future study. 1,1'-Bis(1,2,3,4-tetrahydro-6,7-dimethoxyisoquinoline) was found to readily condense with a wide range of aldehydes to give imidazolines and aspects of the rates of condensation were determined. Mono-alkyl bisisoquinolines were obtained efficiently by cleavage of the imidazolines through a newly defined treatment with sodium cyanoborohydride under acidic conditions. A procedure was developed whereby these two steps could be accomplished in a sequential one-pot process. The mono-alkyl compounds were further derivatized through acetylation, alkylation, sulfonylation and reductive alkylation. Synthetic strategies towards π-excessive N-arenealkyl derivatives were established with the goal to create scaffolds for the coordination of π-deficient systems, of which the X-ray crystal structures of three N-arenemethyl derivatives were elucidated. These are each closely related in conformation about the C1-C1' axis. Reaction of two examples of the N-arenealkyl compounds with copper(II) and palladium(II) chlorides, furnished the first known examples of this type of highly reduced 1,1'-bisisoquinoline-metal complex. Single crystal X-ray crystallography was used to analyse the structures of these complexes in the solid state. Preliminary physicochem…
abstract: The design of partially reduced 1,1'-bisisoquinoline derivatives was investigated with the aim of controlling the conformation about the C1-C1' axis. This would produce ligands with unusual but predictable ligand binding properties, particularly cooperativity. The introduction of ω-aminoalkyl, ω-azidoalkyl, ω-alkynyl and ω-alkenyl groups onto the nitrogens of the reduced bisisoquinoline core was conducted with the intention of broadening the scope of the ligand. Subsequent epoxidation, hydroboration and Huisgen 1,3-dipolar cycloaddition of terminal unsaturated groups and nucleophilic displacement of the chlorine of the corresponding known bischloroacetyl derivative afforded representative examples of new ligand types for future study. 1,1'-Bis(1,2,3,4-tetrahydro-6,7-dimethoxyisoquinoline) was found to readily condense with a wide range of aldehydes to give imidazolines and aspects of the rates of condensation were determined. Mono-alkyl bisisoquinolines were obtained efficiently by cleavage of the imidazolines through a newly defined treatment with sodium cyanoborohydride under acidic conditions. A procedure was developed whereby these two steps could be accomplished in a sequential one-pot process. The mono-alkyl compounds were further derivatized through acetylation, alkylation, sulfonylation and reductive alkylation. Synthetic strategies towards π-excessive N-arenealkyl derivatives were established with the goal to create scaffolds for the coordination of π-deficient systems, of which the X-ray crystal structures of three N-arenemethyl derivatives were elucidated. These are each closely related in conformation about the C1-C1' axis. Reaction of two examples of the N-arenealkyl compounds with copper(II) and palladium(II) chlorides, furnished the first known examples of this type of highly reduced 1,1'-bisisoquinoline-metal complex. Single crystal X-ray crystallography was used to analyse the structures of these complexes in the solid state. Preliminary physicochem…
author: Jones, Michael William
language: EN
keywords: isoquinoline
license: https://purl.org/coar/access_right/c_abf2
license: https://creativecommons.org/licenses/by-nc-nd/3.0/au/
date published: 2005
date modified: 2026-07-24T05:32:27Z
provider: University of New South Wales
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: UNSW, Sydney

PropertyValue
property ID: Handle
value: http://hdl.handle.net/1959.4/27400

PropertyValue
property ID: DOI
value: 10.26190/unsworks/17046