Direct (Hetero)Arylation: A New Tool for Polymer Chemists

The coupling of aryl halides with catalytically activated aryl C–H bondsprovides a desirable and atom-economical alternative to standard cross-coupling reactions for the construction of new C–C bonds. The reaction, termed direct (hetero)arylation, is believed to follow a base-assisted, concerted metalation-deprotonation (CMD) pathway. During this process, carboxylate or carbonate anions coordinate to the metal center, typically palladium, in situ and assist in the deprotonation transition state. Researchers have employed this methodology with numerous arenes and heteroarenes, including substituted benzenes, perfluorinated benzenes, and thiophenes. Thiophene substrates have demonstrated high reactivity toward C–H bond activation when appropriately substituted with electron-rich and/or electron-deficient groups. Because of the pervasive use of thiophenes in materials for organic electronics, researchers have used this chemistry to modularly prepare conjugated small molecules and, more recently, conjugated p...