We showed a straightforward and efficient method for the preparation of the so far unknown parent anti-and syn-dithienopyrazines 5 and 6 including a Pd and ligand-free C-S coupling reaction of ethynylated precursors. The investigation of their electronic properties clearly show stabilization of HOMO and LUMO energy levels and little differences for the two isomers compared to benzodithiophenes and dithienopyridines. This circumstance has consequences on reactivity and regioselectivity of the rather electron-deficient triacenes in, e.g., halogenation, metallation, and redox reactions which allowed for the preparation of valuable halogenated precursors of various substitution patterns for subsequent C-C cross-coupling reactions. To this end, anti-and syn-dithienopyrazines may become reasonable and versatile (acceptor) synthons with potential for novel organic electronic materials. In an upcoming communication we demonstrate that this concept leads to efficient holetransport materials for perovskite solar cells.