Palladium-catalyzed <i>N</i>-arylation of (hetero)aryl chlorides with pyrroles and their analogues

We present a mild and efficient method for the arylation of N-H heteroarenes using a low-loading Pd/keYPhos catalyst (0.8 mol%). This approach employs inexpensive and structurally diverse aryl chlorides as electrophiles in reactions with indoles, pyrroles, and carbazole, enabling the construction of a wide range of <i>N</i>-arylated products. The method exhibits excellent functional group tolerance and is suitable for gram-scale synthesis. Furthermore, the relatively inert Ar-Cl bond allows for late-stage functionalization of pharmaceuticals and stepwise coupling reactions, providing a complementary strategy for the <i>N</i>-arylation of N-H heteroarenes.