Enantiomerization of Axially Chiral Biphenyls: Polarizable MD Simulations in Water and Butylmethylether.
Veronika Zeindlhofer, Phillip Hudson, Ádám Márk Pálvölgyi, Matthias Welsch, Mazin Almarashi, H Lee Woodcock, Bernard Brooks, Katharina Bica-Schröder, Christian Schröder
Author Information
Veronika Zeindlhofer: Department of Computational Biological Chemistry, University of Vienna, Währingerstraße 17, 1090 Vienna, Austria.
Phillip Hudson: Laboratory of Computational Biology, National Heart, Lung, and Blood Institute (NHLBI), National Institutes of Health (NIH), Bethesda, MD 20892, USA.
Ádám Márk Pálvölgyi: Institute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9/163, 1060 Vienna, Austria.
Matthias Welsch: Department of Computational Biological Chemistry, University of Vienna, Währingerstraße 17, 1090 Vienna, Austria.
Mazin Almarashi: Department of Computational Biological Chemistry, University of Vienna, Währingerstraße 17, 1090 Vienna, Austria.
H Lee Woodcock: Department of Chemistry, University of South Florida, Tampa, FL 33620, USA. ORCID
Bernard Brooks: Laboratory of Computational Biology, National Heart, Lung, and Blood Institute (NHLBI), National Institutes of Health (NIH), Bethesda, MD 20892, USA.
Katharina Bica-Schröder: Institute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9/163, 1060 Vienna, Austria.
Christian Schröder: Department of Computational Biological Chemistry, University of Vienna, Währingerstraße 17, 1090 Vienna, Austria.
In this study, we investigate the influence of chiral and achiral cations on the enantiomerization of biphenylic anions in -butylmethylether and water. In addition to the impact of the cations and solvent molecules on the free energy profile of rotation, we also explore if chirality transfer between a chiral cation and the biphenylic anion is possible, i.e., if pairing with a chiral cation can energetically favour one conformer of the anion via diastereomeric complex formation. The quantum-mechanical calculations are accompanied by polarizable MD simulations using umbrella sampling to study the impact of solvents of different polarity in more detail. We also discuss how accurate polarizable force fields for biphenylic anions can be constructed from quantum-mechanical reference data.
