Catalytic Three-component C–C Bond Forming Dearomatization of Bromoarenes with Malonates and Diazo Compounds

Abstract

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.

Catalytic three-component C–C bond forming dearomatization of bromoarenes with malonates and diazo compounds

“…The structural elaboration of the dearomatized products showcase the synthetic utility of the present method. Further studies to develop asymmetric dearomatizations using a chiral catalyst 20 and to elucidate the reaction mechanism are underway in our laboratory. 21…”