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

• Published in: Chemistry : a European journal Vol. 29; no. 60; p. e202301867
• Main Authors: Vogt, Astrid, Stumpges, Florian, Bajrami, Jessi, Baumgarten, Daniel, Millan, Judith, Mena-Osteritz, Elena, Bauerle, Peter
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 26.10.2023
• Subjects: Chemistry; Chemistry, Multidisciplinary; Physical Sciences; Science & Technology; POLYMERS; POLYMERIZATION; ARYLBORONIC ACIDS; FUNCTIONALIZATION; optoelectronic properties; MECHANISTIC ORIGIN; C-H activation; direct arylation; BOND ARYLATION; dithienopyrroles; quantum chemical calculations; DITHIENOPYRROLE; THIOPHENES; POLYCONDENSATION
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202301867

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 beta-arylation and beta,beta'-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 alpha-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 beta-aryl, beta-beta'-diaryl, alpha-aryl, and alpha,alpha'-diaryl scaffolds. These compounds can be straightforwardly prepared and further functionalized for applications as organic electronic materials.