A possibility of non-conventional two-step protonation of 1,8-bis(dimethylamino)naphthalene (proton sponge) is discussed. Unlike the generally accepted mechanism, involving relatively slow direct penetration of a proton into the cleft between the peri-NMe₂ groups, it consists of the rapid addition of a proton to the out-inverted NMe₂ group with the subsequent slower rotational transfer of the proton into the inter-nitrogen space to produce a stable chelated cation. The following approaches were employed during the work: (1) competitive hydrogen bond formation in a specially designed alcohol in which the OH group might chelate either the proton sponge 1-NMe₂ group or another basic center (N,N-dimethylaniline) of known basicity; (2) measuring the basicity of naphtho[1,8-b,c]diazabicyclo[3.3.3]undecane considered to be a close analogue of the proton sponge capable exclusively of out-protonation; (3) X-ray, spectral and DFT studies of structure, energy and stereodynamics of compounds obtained, including their conformers. For the first time, the pK_a value of an organic base with a perfectly flat nitrogen atom is reported. The final conclusion is made that both pathways of proton sponge protonation, traditional and non-conventional, contribute in parallel with a still undefined ratio. The estimated out-basicity of the proton sponge is at least 5.5 orders of magnitude lower than the directly measured in-basicity.

It has been found that 1,8-bis(dimethylamino)naphthalene (DMAN), unlike N,N-dimethylaniline, undergoes ring metallation in the n-BuLi–TMEDA–Et₂O system with a low selectivity and in poor total yields. The situation is significantly improved in the t-BuLi–TMEDA–n-hexane system when 3- and 4-lithium derivatives become the only reaction products obtained in good yields. The formation of 3-Li-DMAN is especially desired since no method of direct meta-functionalization of DMAN is known to date. The relative stability and structure of DMAN lithium derivatives have been examined with the help of X-ray and multinuclear NMR measurements as well as DFT calculations.