Divergent Coupling of Anilines and Enones by Integration of C−H Activation and Transfer Hydrogenation

Cp*Rh III /Ir III complexes are known to play important roles in both C−H activation and transfer hydrogenation (TH). However, these two areas evolved separately. They have been integrated in redox‐ and chemodivergent coupling reactions of N ‐pyridylanilines with enones. The iridium‐catalyzed coupling with enones leads to the efficient synthesis of tetrahydroquinolines through TH from i PrOH. Counterintuitively, i PrOH does not serve as the sole hydride source, and the major reaction pathway involves disproportionation of a dihydroquinoline intermediate, followed by the convergent and iterative reduction of quinolinium species.