The role of lithium cation in the isomerization from diademane to triquinacene and in the Claisen reaction from phenyl allyl ether to 6-allyl-2,4-cyclohexadienone was analyzed. The nature of the interaction of the lithium ion with the reacting molecules in the transition state was studied using supermolecule and perturbational methods. The aromaticity of the transition state in presence of lithium was compared with that for the same reaction in absence of catalyst, employing tools such as nucleus-independent chemical shift and anisotropy of the induced current density. Our results support that the catalytic effect is caused principally by a more favorable electrostatic interaction of lithium cation with the transition states of both reactions.