Synthesis and Crystallographic Characterization of Helical Hairpin Oligourea Foldamers

Abstract

Oligomers designed to form a helix-turn-helix super-secondary structure have been prepared by covalently bridging aliphatic oligourea foldamer helices with either rigid aromatic or more flexible aliphatic spacers. The relative helix orientation in these dimers was investigated at high resolution using X-ray diffraction analysis. In several cases, racemic crystallography was used to facilitate crystallization and structure determination. All structures were solved by direct methods. Well-defined parallel helical hairpin motifs were observed in all cases when 4,4′-methylene diphenyl diisocyanate was employed as a dimerizing agent, irrespective of primary sequence and chain length.