A series of ortho-, meta-, and para-boronic acids and their pinacol esters of 1,8-bis(dimethylamino)naphthalene (DMAN), including the very first naphtho[1,8-cd][1,2,6]oxadiborinine-based proton sponge, were synthesized with moderate to good yields. The ease of deborylation of sterically hindered ortho-boronic acids of DMAN was demonstrated. DMAN-based 3,6-diboronic acid and its pinacol ester─valuable precursors for meta-derivatives of the naphthalene proton sponge─were prepared and utilized for the synthesis of 3,6-diiodo-DMAN. Obtained acids and esters were tested for common palladium and copper catalyzed couplings.