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

Autor: H. Lee Woodcock, Bernard R. Brooks, Katharina Bica-Schröder, Veronika Zeindlhofer, Mazin Almarashi, Ádám Márk Pálvölgyi, Phillip S. Hudson, Matthias Welsch, Christian Schröder
Rok vydání: 2020
Předmět:
chirality transfer
Ionic Liquids
Molecular Dynamics Simulation
010402 general chemistry
01 natural sciences
Article
Catalysis
Inorganic Chemistry
lcsh:Chemistry
chemistry.chemical_compound
Polarizability
Computational chemistry
Quantum Dots
Physics::Atomic and Molecular Clusters
Molecule
Physical and Theoretical Chemistry
Physics::Chemical Physics
Molecular Biology
Conformational isomerism
lcsh:QH301-705.5
Spectroscopy
biphenyl
Biphenyl
Quantitative Biology::Biomolecules
Molecular Structure
010405 organic chemistry
Organic Chemistry
Biphenyl Compounds
Diastereomer
Water
Stereoisomerism
General Medicine
molecular dynamics simulations
chiral ionic liquids
0104 chemical sciences
Computer Science Applications
Solvent
chemistry
lcsh:Biology (General)
lcsh:QD1-999
Umbrella sampling
Chirality (chemistry)
Zdroj: International Journal of Molecular Sciences, Vol 21, Iss 6222, p 6222 (2020)
International Journal of Molecular Sciences
Volume 21
Issue 17
ISSN: 1422-0067
Popis: In this study, we investigate the influence of chiral and achiral cations on the enantiomerization of biphenylic anions in n-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.
Databáze: OpenAIRE
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