Palladium/silver co-catalyzed syn-stereoselective asymmetric ring-opening reactions of azabenzonorbornadienes with amides

Abstract

The first syn-stereoselective generation of 1,2-diamino dihydronaphthalene derivatives by asymmetric ring-opening reaction of azabenzonorbornadienes is reported. Electron-deficient amides have been successfully employed as nucleophiles in the aromatic ring-opening reaction of azabenzonorbornadienes. The reaction was co-catalyzed by Pd(OAc)₂ and AgBF₄ with (R)-BINAP as the chiral ligand. The ARO products were obtained in good to high yields (up to 96%) with excellent enantioselectivities (up to 98%).