Enantiomerization of Axially Chiral Biphenyls: Polarizable MD Simulations in Water and Butylmethylether

• Published in: International journal of molecular sciences Vol. 21; no. 17; p. 6222
• Main Authors: Zeindlhofer, Veronika, Hudson, Phillip, Pálvölgyi, Ádám Márk, Welsch, Matthias, Almarashi, Mazin, Woodcock, H Lee, Brooks, Bernard, Bica-Schröder, Katharina, Schröder, Christian
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 28.08.2020; MDPI
• Subjects: Anions; biphenyl; Biphenyl Compounds - chemistry; Catalysis; Cations; chiral ionic liquids; Chirality; chirality transfer; Complex formation; Experiments; Free energy; Hydrogen; Hydrogenation; Influence; Ionic Liquids - chemistry; Ligands; Molecular Dynamics Simulation; molecular dynamics simulations; Molecular Structure; Polarity; Quantum Dots; Simulation; Solvents; Stereoisomerism; Water - chemistry; molecular dynamics simulations; biphenyl; chiral ionic liquids; chirality transfer
• ISSN: 1422-0067; 1661-6596; 1422-0067
• DOI: 10.3390/ijms21176222

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.