Amino acid ferrocene conjugates using sulfonamide linkages

Abstract

This report presents the synthesis and characterization of mono- and bis(amino acid ester) ferrocene complexes generated using a sulfonamide linking strategy as an alternative to the more heavily explored amide linking strategy. These compounds were investigated to test their ability to form hydrogen bonding interactions both in the solid state and in solution, and were compared to the previously observed intramolecular interstrand crosslinking seen in amide-linked ferrocene constructs. Synthesized compounds also included controls that do not exhibit sulfonamide N-H bonds and thus cannot engage in hydrogen bonding. In the solid state, we observe both S=O⋯H-N and C=O⋯H-N intermolecular interactions, but we do not observe any intramolecular interstrand hydrogen bonding. In the solution phase, we also do not see any intramolecular hydrogen bonding interactions in these compounds as measured by titration of d6-DMSO as a competitive hydrogen bonding reagent. We also collected CD spectra on these compounds, which revealed that the chiral peptides can induce dichroism in the d-d transition of the ferrocene units. Our results indicate that the peptide-ferrocene linking group governs whether intermolecular hydrogen bonding interactions can occur between the amino acids adjacent to the cyclopentadienyl groups.