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

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

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 functionalization. number Co(III) have been structurally characterized, including, for first time aminoquinoline system, complexes arising from migratory insertion cobalt–carbon bonds. The stoichiometric reactions cobalt(III) aryls with alkenes, alkynes, carbon monoxide, cyclic secondary amines, benzamides explored. oxidation state cobalt product-forming step depends on nature coupling component. Specifically, annulation alkynes carbonylation CO likely proceed via Co(I)/Co(III) cycle. Carbon–hydrogen alkenes as well benzamide homocoupling, (formally) Co(IV) species involve oxidatively induced reductive elimination.

Language: Английский

Insights into the mechanism of 3d transition-metal-catalyzed directed C(sp³)–H bond functionalization reactions

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review provides an overview of the research advaces in Ni-, Cu-, Fe- and Co-catalyzed directed C(sp 3 )–H bond functionalization reactions; including design principles, mechanistic discussions, along with potential applications limitations.

Language: Английский

Exploration of Organometallic Cobalt Intermediates in an Aminoquinoline-Directed Dehydrogenative Dimerization Reaction

Organometallics, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 16, 2024

Language: Английский