A Pd-catalyzed dearomative three-component C–C bond formation of bromoarenes with diazo compounds and malonates was developed. Various bromoarenes ranging from benzenoids to azines and heteroles were transformed to the corresponding...

A Pd-catalyzed dearomative three-component C–C bond formation of bromoarenes with diazo compounds and malonates was developed. Various bromoarenes ranging from benzenoids to azines and heteroles were transformed to the corresponding substituted alicyclic molecules. The key of this reaction is the generation of a benzyl-palladium intermediate, which reacts with malonates to form a Pd–<i>O</i>-enolate species. Strikingly, the present method enabled rapid access to multi-substituted alicycles through subsequent elaboration of dearomatized products.

A Pd-catalyzed dearomative three-component C–C bond formation of bromoarenes with diazo compounds and malonates was developed. Various bromoarenes ranging from benzenoids to azines and heteroles were transformed to the corresponding substituted alicyclic molecules. The key of this reaction is the generation of a benzyl-palladium intermediate, which reacts with malonates to form a Pd–<i>O</i>-enolate species. Strikingly, the present method enabled rapid access to multi-substituted alicycles through subsequent elaboration of dearomatized products.