A reactivity optimization study of the palladium-catalyzed cross-coupling reactions of 2, 3- dibromothiophene and organometallic reagents has been conducted. Regioselective coupling at the C2 position, accomplished most notably by Suzuki coupling, was combined with a Stille reaction at C3 using Fu's modification, to afford the 2, 3-disubstituted thiophene derivatives.