Synthesis and Characterization of Naphtho[2,1‐b:7,8‐b′]bis[1]benzothiophene

We describe a simple three‐step synthesis of naphtho[2,1‐b:7,8‐b′]bis[1]benzothiophene, which is scalable to multi‐hundred‐gram. We report the subsequent functionalization of this compound into iodine, boronic ester and silane derivatives, which are useful intermediates for various applications. The core structure was analyzed by NMR and single‐crystal X‐ray diffraction, and the physical properties were investigated by cyclic voltammetry, UV/Vis‐ and fluorescence spectroscopy. Naphtho[2,1‐b:7,8‐b′]bis[1]benzothiophene is synthesised in three steps on a multi‐hundred‐gram scale. Subsequent functionalization of the compound yields the iodine, boronic ester and silane derivatives, which are valuable intermediates for subsequent coupling reactions.