Ambidextrous Catalytic Access to Dithieno[3,2-b:2′,3′-d]thiophene (DTT) Derivatives by Both Palladium-Catalyzed C-S and Oxidative Dehydro C-H Coupling

A modular two-step synthesis of dithieno[3,2-b:2',3'-d]thiophene (DTT) derivatives by C-S cross-coupling and oxidative dehydro C-H coupling is herein described. Dibenzo[d,d']thieno[3,2-b;4,5-b']dithiophene (DBTDT) and associated two donor (anisyl) and acceptor (acetyl) substituted DTT derivatives were synthesized by palladium-catalyzed cross-coupling sequences in 17% to 71% yield over two steps. The 5,5'-disubstituted DTT derivatives were characterized in terms of their photophysical (UV and fluorescence spectroscopy) and electrophysical (cyclovoltammography) properties.