Cooperative Base-Metal Catalysis for Decarboxylative Olefination of Carboxylic Acids

Abstract

Cooperative catalytic systems that merge base-metal radical generation with transition-metal-mediated reactivity provide opportunities for chemical synthesis but remain challenging to design because they require productive redox communication between distinct metal manifolds. Herein, we report a cooperative Fe/Co catalytic platform for the direct decarboxylative olefination of carboxylic acids under light irradiation. The reaction combines iron-mediated ligand-to-metal charge transfer (LMCT) radical generation with cobalt-catalyzed dehydrogenation, converting diverse carboxylic acids, including industrially relevant fatty acids and complex bioactive derivatives, into olefins. Kinetic, spectroscopic, spin-trapping, and DFT studies support a symbiotic pathway in which DBU acts as both a Brønsted base and a redox-active mediator interconnecting the iron and cobalt cycles. This work establishes cooperative Fe/Co catalysis as an inner-sphere manifold distinct from conventional outer-sphere photoredox catalysis and provides a design principle for interdependent base-metal radical catalysis.