Remote Control of the Planar Chirality in Peptide-Bound Metallomacrocycles and Dynamic-to-Static Planar Chirality Control Triggered by Solvent-Induced 3(10)-to-α-Helix Transitions

Angew Chem Int Ed Engl. 2015 Nov 23;54(48):14442-6. doi: 10.1002/anie.201507918. Epub 2015 Oct 1.

Abstract

The dynamic planar chirality in a peptide-bound Ni(II)-salphen-based macrocycle can be remotely controlled. First, a right-handed (P)-3(10)-helix is induced in the dynamic helical oligopeptides by a chiral amino acid residue far from the macrocyclic framework. The induced planar chirality remains dynamic in chloroform and acetonitrile, but is almost completely locked in fluoroalcohols as a result of the solvent-induced transition of the peptide chains from a 3(10)-helix to a wider α-helix, which freezes the rotation of the pendant peptide units around the macrocycle.

Keywords: chirality; macrocycles; peptides; self-assembly; supramolecular chemistry.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Macrocyclic Compounds / chemistry*
  • Metals / chemistry*
  • Peptides / chemistry*
  • Solvents / chemistry
  • Stereoisomerism*

Substances

  • Macrocyclic Compounds
  • Metals
  • Peptides
  • Solvents