Whereas standard strong bases (n-BuLi, s-BuLi/TMEDA, n-BuLi/t-BuOK, TMPMgCl· LiCl, and LDA) reduce the N N bond of the parent azobenzene (Y= H), aromatic H→ Li permutation occurs with LTMP when a suitable director of lithiation (Y= OMe, CONEt2, F) is present in the benzene residue of the azo compound. The method allows direct access to new substituted azobenzenes.