The first to report on the relationship between kinetic and thermodynamic control were R.B. Woodward and Harold Baer in 1944. They were re-investigating a reaction between maleic anhydride and a fulvene first reported in 1929 by Otto Diels and Kurt Alder. They observed that while the endo isomer is formed more rapidly, longer reaction times, as well as relatively elevated temperatures, result in higher exo / endo ratios which had to be  considered in the light of the remarkable stability of the exo-compound on the one hand and the very facile dissociation of the endo isomer on the other.
C. K. Ingold with E. D. Hughes and G. Catchpole independently described a thermodynamic and kinetic reaction control model in 1948. They were reinvestigating a certain allylic rearrangement reported in 1930 by Jakob Meisenheimer. Solvolysis of gamma-phenylallyl chloride with AcOK in acetic acid was found to give a mixture of the gamma and the alpha acetate with the latter converting to the first by equilibration. This was interpreted as a case in the field of anionotropy of the phenomenon, familiar in prototropy, of the distinction between kinetic and thermodynamic control in ion-recombination.