Selective Palladium-Catalyzed Direct Arylation of Furo[3,2-b]pyridines

A method for palladium-catalyzed direct arylation has been developed for the selective functionalization of the C-3 and C-7 positions of 2-substituted furo[3,2-b]pyridines. An unconventional reactivity resulting from the annulation of a pyridine ring with a furan ring is outlined and results in an unprecedented C-7?H bond activation. The role of the pivalic acid additive is rationalized by invoking a concerted metallationdeprotonation pathway (CMD) for both arylations.