A cobalt-diphosphine catalyst promotes the addition of an arylzinc reagent to a norbornene derivative to afford o-(2-exo-norbornyl)arylzinc species. This “migratory arylzincation” reaction is considered to involve insertion of norbornene into an arylcobalt species, alkyl-to-aryl 1,4-cobalt migration, and transmetalation between the resulting o-(2-exo-norbornyl)arylcobalt species and the arylzinc reagent. The o-(2-exo-norbornyl)arylzinc species can be intercepted by common organic electrophiles under copper or palladium catalysis.