ABSTRACT Chiral solvating agents are widely used for enantiomeric discrimination in NMR spectroscopy. In some cases, though, the enantiomeric discrimination is small or non-existent in the resulting NMR spectra. It is often possible to enhance the discrimination by coupling paramagnetic lanthanide ions to the chiral solvating agent. One way to couple a lanthanide ion to a chiral solvating agent is to simply mix the species in solution. Assuming the enantiomers exhibit different association constants with the solvating agent, and assuming the lanthanide preferentially binds to the substrate, the spectrum of the enantiomer with the weaker association with the solvating agent exhibits the larger lanthanide-induced shifts. Alternatively, lanthanide ion can be bonded to solvating agents that have been modified to include a chelating ligand. Covalent attachment of lanthanide ions not only results in more effective chiral NMR shift reagents, but the predictable nature of the lanthanide-induced shifts provides a means to study the geometry of interaction of substrates with the chiral solvating agents. Coupled systems employing cyclodextrins, crown ethers, and donor-acceptor chiral solvating agents are described.
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