Chiral information harvesting in dendritic metallopeptides

Author:  ["Naoki Ousaka","Yuki Takeyama","Hiroki Iida","Eiji Yashima"]

Publication:  Nature Chemistry

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Tags:     Chemistry

Abstract

Long-range communication of stereochemical information is common in biological systems, particularly in enzyme-catalysed reactions. Here, we report the remote control of the dynamic chirality of metal centres, coordinated by 2,2′-bipyridine ligands bearing dynamic helical oligopeptides. The helical chirality of the oligopeptides is controlled by a stereocentre remote from the metal. We show that when a mixture of chiral and achiral peptide ligands is used, both the chirality of the metal centre and that of the achiral oligopeptide helices are significantly amplified. The amplification mechanism relies on several steps of chirality induction, first from a single chiral peptide to the helicity of an oligopeptide through the induction of propeller chirality at the metal centre, then on to induction of helical chirality in an achiral oligopeptide. 2,2′-bipyridine ligands coordinate to metals to form chiral propeller-like complexes. Now, this chirality is shown to be controlled by the coordination of 2,2′-bipyridine ligands that bear helical oligopeptides, which incorporate chiral amino acids at positions remote from the metal centre. This chirality is further translated, via the metal centre, to other achiral-oligopeptide-containing ligands.

Cite this article

Ousaka, N., Takeyama, Y., Iida, H. et al. Chiral information harvesting in dendritic metallopeptides. Nature Chem 3, 856–861 (2011). https://doi.org/10.1038/nchem.1146

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