Tunable Regioselectivity in C−H‐Activated Direct Arylation Reactions of Dithieno[3,2‐ b :2’,3’‐ d ]pyrroles

In this study, regioselectively controlled direct arylation of dithieno[3,2‐ b :2,3’‐ d ]pyrroles (DTPs) is reported. By carefully selecting the catalytic system, Pd source, ligand, and additives, we achieved either selective N‐arylation or unprecedented β‐arylation and β,β′‐diarylation of the DTP core through C−H activation when reacting unsubstituted H ‐DTP with 9‐anthracenyl halides. For N‐substituted DTPs, we obtained regioselective carboxylate‐assisted arylation of the α‐position(s). Consequently, depending on the catalytic system and substitution at the DTP nitrogen, we successfully synthesized novel regioselectively substituted DTPs, including N‐aryl, rarely reported β‐aryl, β,β’‐diaryl, α‐aryl, and α,α‘‐diaryl scaffolds. These compounds can be straightforwardly prepared and further functionalized for applications as organic electronic materials.