An outstanding and very rare example of the full kinetic and thermodynamic reaction control in the process of the tandem inter-/intramolecular Diels–Alder reaction of bis-furyl dienes 3 with hexafluoro-2-butyne or dimethyl acetylenedicarboxylate (DMAD) have been discovered and described in 2018. At low temperature, the reactions occur chemoselectively leading exclusively to adducts of pincer-[4+2] cycloaddition (5). The exclusive formation of domino -adducts (6) is observed at elevated temperatures.