AbstractThis report examines the effect of substrate design upon the TruceâSmiles rearrangement, an intramolecular nucleophilic aromatic substitution reaction. The length of the molecular spacer that tethers the carbanion nucleophile to the substituted benzene ring was found to have a strong influence on the ability of the substrate to undergo the reaction successfully. Our experimental results show highest yield of desired aryl migration product for substrates designed with a 3âatom tether, which proceed through a 5âmembered spirocyclic intermediate. The results are interpreted in comparison with a survey of TruceâSmiles rearrangements described in the literature and found to be consistent. Computational studies support the observed reactivity trend and suggest an explanation of a favorable combination of ring strain and electrostatic repulsion leading to optimal reactivity of the substrate designed with a 3âatom tether. Comparison of our results with trends for related ringâclosing reactions illustrate the unique electrostatic features of the system studied herein.