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Computational Prediction and Rationalization, and Experimental Validation of Handedness Induction in Helical Aromatic Oligoamide Foldamers
Author(s) -
Liu Zhiwei,
Hu Xiaobo,
Abramyan Ara M.,
Mészáros Ádám,
Csékei Márton,
Kotschy András,
Huc Ivan,
Pophristic Vojislava
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201605082
Subject(s) - chemistry , metadynamics , steric effects , hydrogen bond , circular dichroism , chirality (physics) , monomer , molecular dynamics , conformational isomerism , stereochemistry , computational chemistry , molecule , organic chemistry , polymer , nambu–jona lasinio model , chiral symmetry breaking , physics , quantum mechanics , quark
Metadynamics simulations were used to describe the conformational energy landscapes of several helically folded aromatic quinoline carboxamide oligomers bearing a single chiral group at either the C or N terminus. The calculations allowed the prediction of whether a helix handedness bias occurs under the influence of the chiral group and gave insight into the interactions (sterics, electrostatics, hydrogen bonds) responsible for a particular helix sense preference. In the case of camphanyl‐based and morpholine‐based chiral groups, experimental data confirming the validity of the calculations were already available. New chiral groups with a proline residue were also investigated and were predicted to induce handedness. This prediction was verified experimentally through the synthesis of proline‐containing monomers, their incorporation into an oligoamide sequence by solid phase synthesis and the investigation of handedness induction by NMR spectroscopy and circular dichroism.