Palladium(II) Catalyst Systems for the Addition of Boronic Acids to Bicyclic Alkenes:  New Scope and Reactivity

[reaction: see text] The palladium-catalyzed ring-opening addition of arylboronic acids to heterobicyclic alkenes is reported. Excellent yields are obtained for the addition of a wide variety of arylboronic acids to aza- and oxabicyclic alkenes. This methodology is especially useful in the synthesis of 1-amino-2-aryldihydronaphthalene scaffolds, for which rhodium catalysts are currently unreactive or give complex mixtures. Asymmetric versions of these reactions are under development, and preliminary results are reported.