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.
Anion-triggered chiral switch: Reversible switching between fac and mer isomers in tris(2,2'-bipyridine)iron(II) complexes, the ligands of which are substituted at the 5-position with various peptides of different lengths and sequences, has been achieved (see figure). The remote stereocontrol at the Fe II center by a domino-type chiral information transfer along an achiral peptide main-chain was observed even over 3 nm (50 bond lengths). Ringing the changes: Selenazolines have applications in medicinal chemistry, but their synthesis is challenging. We report a new convenient and less toxic route to these heterocycles that starts from commercially available selenocysteine. The new route depends on a heterocyclase enzyme that creates oxazolines and thiazolines from serines/ threonines and cysteines.ChemBioChem
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