Enaminone-directed ruthenium(II)-catalyzed C-H activation and annulation of arenes with diazonaphthoquinones for polycyclic benzocoumarins.

The weakly coordinating enaminone functionality has been leveraged for a C-H bond activation strategy under ruthenium catalysis and employed in the regioselective annulative coupling of arenes with diazonaphthoquinones, offering polycyclic benzocoumarins in very high yields. The enaminone motif plays a dual role and the protocol operates through a Ru(II)/Ru(IV) catalytic pathway which is amenable to the diversification of various pharmacophore-coupled substrates.