This study reports the first example of using a dual catalytic system with copper(II) acetate and 2-hydroxynicotinaldehyde to achieve transient C(sp2)–H sulfonylation of benzylamines with sulfinate salts via a dynamically formed imine directing group. Manganese(IV) oxide was identified as an effective oxidant and base. Computational DFT investigations suggest that the TDG lowers the energy barrier for an acetate-mediated, turnover limiting C–H activation step and subsequent combination of the cupracycle with a RSO2 radical.