A Computational/Experimental Investigation into the Reversibility of [6+4]/[4+2] Cycloadditions with Tropone Derivatives

for the reactions of some tropone derivatives with cyclopentadiene. Likewise, calculations provide reasonable predictions of the distribution of [6+4] and competitive [4+2] adducts, with [6+4] adducts converting to the more stable [4+2] adducts at elevated temperatures. Finally, we observe that even the rather stable [4+2] adducts show partial reversion to the starting tropone. Due to the alignment between calculations and experimental kinetic and thermodynamic data, this work highlights the value of employing DFT methods to help, in the future, in the design of new reversible cycloadditions.