Syntheses and studies of sapphyrins and anion receptors

Abstract

Polypyrrolic (or aromatic) macrocycles have attracted considerable recent interest due to their potential utility in various applications, including as novel materials, anion receptors, and therapeutic leads. In order to explore further the range and utility of this generalized class of molecules, various sapphyrin and sapphyrin analogues were synthesized. Among the new compounds prepared is an inverted sapphyrin, a species that displayed weak, but noticeable aromaticity. Another new system, benzoxasapphyrin was found to display a reduced anion binding affinity compared to other analogous macrocycles. Finally, several derivatized sapphyrins were prepared as potential anticancer leads. Separate from the above, efforts were made to develop anion receptors based on the indole motif. This substructure plays a key role is stabilizing a range of non-covalent interactions in complex biological structures. However, prior to the present study, indole-type hydrogen bonding donors had not been widely used to prepare synthetic anion receptors. Accordingly, a diindolyl quinoxaline system was prepared; it served to demonstrate that small molecule indole receptors can effectively bind phosphate anions in organic media. Finally, a set of cyanide anion indicators were prepared; these were predicated on the use of a cyanide-specific reaction, namely the benzil rearrangement reaction. The benzil reaction-based indicators produced in this way were found to be quite selective for the cyanide anion in organic solvents. Further, their study helped provide insights into the mechanism of this as-yet not fully studied reaction. In the context of developing this specific anion indicator, a review of other reaction-based indicators was reviewed. This is provided in Chapter 3.