Direct Access to Nitrogen Bi-heteroarenes via Iridium-Catalyzed Hydrogen-Evolution Cross-Coupling Reaction.

Through cooperative actions of iridium catalyst and NaOTf additive we report a new direct access to nitrogen bi-heteroarenes via hydrogen-evolution cross-coupling of the β-site of indoles/pyrrole with the α-site of N-heteroarenes. The reaction proceeds in an atom- and redox-economic fashion together with the merits of an easily available catalyst system, broad substrate scope, excellent functional tolerance, and no need for external oxidants, offering a practical way to create π-conjugated systems.