Separation and Complete Analyses of the Overlapped and Unresolved $^1H$ NMR Spectra of Enantiomers by Spin Selected Correlation Experiments

Prabhu, Uday Ramesh and Baishya, Bikash and Suryaprakash, N (2008) Separation and Complete Analyses of the Overlapped and Unresolved $^1H$ NMR Spectra of Enantiomers by Spin Selected Correlation Experiments. In: Journal of Physical Chemistry A, 112 (25). pp. 5658-5669.

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Abstract

NMR spectroscopic discrimination of optical enantiomers is most often carried out using $^2H$ and $^{13}C$ spectra of chiral molecules aligned in a chiral liquid crystalline solvent. The use of proton NMR for such a purpose is severely hindered due to the spectral complexity and the significant loss of resolution arising from numerous short- and long-distance couplings and the indistinguishable overlap of spectra from both R and S enantiomers.The determination of all the spectral parameters by the analyses of such intricate NMR spectra poses challenges,such as, unraveling of the resonances for each enantiomer, spectral resolution, and simplification of the multiplet pattern. The present study exploits the spin state selection achieved by the two-dimensional $^1H$ NMR correlation of selectively excited isolated coupled spins (Soft-COSY) of the molecules to overcome these problems. The experiment provides the relative signs and magnitudes of all of the proton-proton couplings, which are otherwise not possible to determine from the broad and featureless one-dimensional $^1H$ spectra. The utilization of the method for quantification of enantiomeric excess has been demonstrated. The studies on different chiral molecules, each having a chiral center, whose spectral complexity increases with the increasing number of interacting spins, and the advantages and limitations of the method over SERF and DQ-SERF experiments have been reported in this work.

Item Type:	Journal Article
Publication:	Journal of Physical Chemistry A
Publisher:	American Chemical Society
Additional Information:	Copyright of this article belong to American Chemical Society.
Department/Centre:	Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited:	17 Jul 2008
Last Modified:	19 Sep 2010 04:47
URI:	http://eprints.iisc.ac.in/id/eprint/15069

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