Catalytic Carbo- and Aminoboration of Alkenyl Carbonyl Compounds via Five- and Six-Membered Palladacycles

A palladium­(II)-catalyzed alkene difunctionalization reaction has been developed, wherein B2pin2 is used to trap chelation-stabilized alkylpalladium­(II) intermediates that are formed upon nucleopalladation. A range of carbon and nitrogen nucleophiles were found to be suitable coupling partners in this transformation, providing moderate to high yields. Both 3-butenoic and 4-pentenoic acid derivatives were reactive substrate classes, affording β,γ- and γ,δ-difunctionalized carboxylic acid derivatives. This work represents a new strategy to synthesize highly functionalized secondary boronates that complements existing methods.