Mechanistic Investigations of Cobalt-Catalyzed, Aminoquinoline-Directed C(sp²)-H Bond Functionalization

Monoanionic, bidentate-auxiliary-directed, cobalt-catalyzed C-H bond functionalization has become a very useful tool in organic synthesis. A comprehensive investigation into isolated organometallic intermediates and their reactivity within the catalytic cycle is lacking. We report here mechanistic studies of cobalt-catalyzed, aminoquinoline-directed C(sp²)-H bond functionalization. A number of organometallic Co(III) intermediates have been isolated and structurally characterized, including, for the first time in the aminoquinoline system, complexes arising from migratory insertion into cobalt-carbon bonds. The catalytic and stoichiometric reactions of cobalt(III) aryls with alkenes, alkynes, carbon monoxide, cyclic secondary amines, and aminoquinoline benzamides have been explored. The oxidation state of cobalt intermediates in the product-forming step depends on the nature of the coupling component. Specifically, annulation with alkynes and carbonylation with CO likely proceed via a Co(I)/Co(III) catalytic cycle. Carbon-hydrogen bond functionalization with alkenes and amines, as well as benzamide homocoupling, likely proceed via a (formally) Co(IV) species and involve oxidatively induced reductive elimination.