[en] The aminolysis of phenyl dithiocyclohexane-carboxylates with anilines in acetonitrile proceeds by rate-limiting breakdown of a tetrahedral intermediate, T^±. The large β_X (β_nuc) values can be accounted for by a strong localized cationic charge on the nitrogen atom of anilines in T^±, which is lost in the aniline expulsion from T^± (k_-a). The breakdown rate ratio of k_-a/k_b is large due to large k_-a and relatively small k_b. The proposed mechanism is also supported by a large positive cross-interaction constant, ρ_XZ (= 1.68), adherence to the RSP, and low activation parameters. The greater than unity k_H/k_D values involving deuterated anilines suggests a four-center type hydrogen-bonded TS