We demonstrate here a new variant on a statistical spectroscopic method for recovering structural information on unstable intermediates formed in reaction mixtures. We exemplify this approach with respect to the internal acyl migration reactions of 1-beta-O-acyl glucuronides (AGs), which rearrange at neutral or slightly alkaline pH on a minute to hour time scale to yield a series of positional glucuronide ring isomers and alpha/beta anomers from the 1-beta (starting material), i.e. 2-beta, 2-alpha, 1-alpha, 3-beta, 3-alpha, and 4-beta, 4-alpha isomers together with the aglycon and alpha- and beta-glucuronic acid hydrolysis products. Multiple sequential 800 MHz cryoprobe (1)H NMR spectra (1D and 2D J-resolved, JRES) were collected on a 5.1 mM solution of a synthetic model drug glucuronide, 1-beta-O-acyl (S)-alpha-methyl phenylacetyl glucuronide (MPG) in 0.1 M sodium phosphate buffer in D2O at pD 7.4 over 18 h to monitor the reaction which leads to the formation of the eight positional isomers and hydrolysis products. As the reaction proceeds and new isomers form, the NMR signal intensities vary accordingly allowing the application of a novel kinetic variant on statistical total correlation spectroscopy (K-STOCSY) method to recover the connectivities between proton signals on the same reacting molecule based on their intensity covariance through time. We performed K-STOCSY analysis on both the standard 1D NMR spectra and the skyline projected singlets of the (1)H-(1)H JRES NMR spectra through time, i.e. the K-JRES-STOCSY experimental variant, which increases the effective spectral dispersion and is ideally suited for the analysis of heavily overlapped spin systems. High statistical correlations were observed between mutarotated alpha- and beta-anomers of individual positional isomers, as well as directly acyl migrated products and anticorrelation observed between signals from compounds that were being depleted as others increased, e.g. between the 1-beta and 2-alpha/2-beta isomers. This statistical kinetic approach enabled the recovery of structural connectivity information on all isomers allowing unequivocal resonance assignment, and this approach to spectroscopic information recovery has wider potential uses in the study of reactions that occur on the second-to-minute time scale in conditions where multiple sequential NMR spectra can be collected. JRES-STOCSY is also of potential use as a method for recovering spectroscopic information in highly overlapped NMR signals and spin systems in other types of complex mixture analysis.