In this thesis, it has been demonstrated that 6- and 7-azaindoles with various substituents could be prepared by conjugate additions of (N-formyl)-2-amino-3 iodopyridine and (N-formyl)-3-amino-4-iodopyridine to acetylenic sulfones, ynoates and ynones, followed by copper-mediated intramolecular cyclizations of the resulting o-haloaryl enamine adducts. This methodology employs DMF-water as the solvent and copper(II) acetate as the catalyst for the cyclization step. Neither added ligands nor the exclusion of oxygen is necessary. The process therefore provides a simple, convenient, and inexpensive route to this biologically interesting class of products.
Attempts to improve the yields of azaindole products lacking substituents at C-2, or to access the deazapurine and dihydroquinoline/dihydroisoquinoline motifs, proved to be problematic, because of difficulty in effecting the corresponding conjugate additions in reasonable yields, or because the subsequent copper-catalyzed cyclizations could not be carried out under the usual conditions.