Date of Award
Winter 1998
Project Type
Dissertation
Program or Major
Chemistry
Degree Name
Doctor of Philosophy
First Advisor
G R Weisman
Abstract
A new methodology for the preparation of tetraazamacrocycles is presented. This new methodology utilizes a regioselective reduction of vicinal bisaminals (33) and bisamidines (16) precursors to afford ring expanded tetraamines. This chemistry has provided a synthetic route for the preparation of benzocyclam (34), a compound whose preparation is unreported in the literature.*.
This methodology has aided in the preparation of cross-bridged cyclam derivatives (83, 92, 95). Cross-bridged cyclam derivatives are bicyclic tetraamines which adopt low energy conformations appropriate for the complexation of small cations. Cross-bridged cyclam derivatives have potential utility in clinical and nuclear medicine as well as bioinorganic chemistry. The preparation of new derivatives of cross-bridged cyclam and studies on their chemistry are presented.*.
Cross-bridged cyclam derivatives are good complexers of Li+. In fact, cross-bridged cyclam derivatives complex Li+ selectively over Na+. Ligands which can selectively bind Li+ in the presence of Na+ would have significant utility as Li + sensors which could monitor small concentrations of Li+ in the presence of abundant Na+. Experiments on the relative selectivity for cross-bridged cyclam ligands for Li+ and Na + as well as the relative complexation ability between ligands is presented.
Recommended Citation
Reed, David Philip, "Synthesis of vicinal bisamidines and bisaminals for the preparation of tetraazamacrocycles and the synthesis of cross-bridged cyclam derivatives and studies on their complexation of small cations" (1998). Doctoral Dissertations. 2057.
https://scholars.unh.edu/dissertation/2057