A Direct, Regioselective Palladium-Catalyzed Synthesis of N-Substituted Benzimidazoles and Imidazopyridines

Unsymmetric, N‐substituted benzimidazoles and imidazopyridines can be prepared directly from 2‐halonitroarenes and amides through Pd(TFA)2/(R)‐BINAP‐catalyzed cross‐coupling and subsequent reductive aminocyclization. This sequence can be conducted by a one‐pot procedure. The method is versatile and allows the straightforward, regioselective preparation of these important nitrogen heterocycles. Unsymmetrical, N‐substituted benzimidazoles can be prepared directly from 2‐halonitroarenes and amides through Pd(TFA)2/(R)‐BINAP‐catalyzed cross‐coupling and subsequent reductive aminocyclization.This sequence can be conducted by a one‐pot procedure. The method is versatile and allows the straightforward, regioselective preparation of these important nitrogen heterocycles.