Catalytic enantioselective ring-opening of oxa-and aza-bicyclic alkenes with readily available accessible alkenylboronic acids,pro-moted by a chiral phosphine-Co complex,is reported.Such a process represents the unprecedented Co-catalyzed introduction of various alkenyl groups onto the oxa-and aza-bicyclic alkenes,affording a wide range of multisubstituted functionalized cyclohexenes in up to 98% yield and 99.5 :0.5 er.