Superknock propensity in a stoichiometric dimethyl-ether (DME)/air mixture with temperature inhomogeneities under realistic IC engine conditions is investigated using two-dimensional direct numerical simulations (DNS). The developing detonation regime at different conditions is identified by varying the initial mean temperature lying in the low-, intermediate-, and high-temperature chemistry regimes, the level of temperature fluctuations, and its characteristic length scale. We found that the cool flame from the first-stage ignition induces synergistic effects on promoting knock tendency. First, it significantly decreases a minimum run-up distance requirement for developing detonation due to the low-temperature chemistry. Second, analyzing the temporal evolution of the spatial distribution of ignition delay field reveals that the heat release rate from the first-stage ignition effectively modifies the initial field of the ignition delay time, thereby shifting the mixture towards the developing detonation regime. The interaction of multiple ignition kernels is also found to play an important role in enhancing the onset of detonation.