Synthesis of bioconjugated sym -pentasubstituted corannulenes: Experimental and theoretical investigations of supramolecular architectures

Abstract

Applications of supramolecular architectures span a broad range of fields from medicinal chemistry to materials science and gas storage, making the design and synthesis of such structures a goal of high interest. The unique structural and symmetric properties of corannulene and the recent synthetic developments of C5-symmetric pentafunctionalized derivatives motivate efforts to synthesize bioconjugated-corannulene systems and investigate their supramolecular assembly properties. Herein is presented the synthesis of sym-pentasubstituted corannulenes functionalized with sugar (galactose and ribose), oligopeptide, nucleosides (thymidine and deoxyadenosine), and palindromic oligonucleotide strands. Experimental and theoretical results demonstrate capability of supramolecular assembly formation in these constructs. Ab initio theoretical modeling enables further evaluation of structure and energetics of oligonucleotide-functionalized corannulene formation. Results indicate formation of aggregates, although icosahedral supramolecular formation is not observed. Analyses suggest future improvements to synthetic routes to achieve icosahedral architectures. © 2013 American Chemical Society.