Abstract
NMR 31P-{ 1H} spectra of stereoisomeric N - [S - (methylethoxyphosphinyl) - thioglycolyl]valines in solution to reveal association of the molecules, and interaction of the chiral centres. Under fast inter-associate exchange in achiral media, these interactions lead to the following: (i) The chemical shift of the racemic mixture of enantiomers deviates from the shift of the individual species; (ii) the spectra of non-racemic mixtures are doublets; (iii) there are 2 n lines in the spectrum of a mixture containing unequal concentrations of stereoisomers with n asymmetric centres. The integrated intensity ratio is equal to the concentration ratio in all cases. The concept of statistically controlled associate diastereomerism (SCAD) is introduced and the respective formalism is given to describe the spectral effects accompanying variations of temperature and concentration. It is also shown applicable to more complicated cases involving ion exchange of chiral fragments between stereoisomers.
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