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.
Nitrogen-containing molecules are ubiquitous in pharmaceuticals, agrochemicals, and functional materials, making the development of efficient C─N bond-forming reactions a central goal in synthesis. Cobalt-catalyzed metal-hydride hydrogen atom transfer (Co─H/MHAT) has emerged as a powerful platform for alkene hydroamina...
Radical-mediated transition-metal-catalyzed C─H carbonylation represents a direct and powerful approach for the synthesis of carbonyl compounds; however, the stoichiometric oxidants typically required for hydrogen atom abstraction hamper the extensive application of these protocols and raise environmental concerns. In...
Cheng-Cheng Fan, Jia-Ning Wu, Peng Wang et al.· Angewandte Chemie· 0 citations
Metal-organic frameworks (MOFs) offer a structurally tunable platform for photocatalysis, yet their activity for hydrogen evolution is often constrained by inefficient charge separation and reliance on metal cocatalysts. Herein, a family of MOFs, BVR-19-M, constructed from divalent transition metal ions (M = Mg2+, Mn...
E. N. Musa, Galen J. Fritz, Dylan Pyle et al.· Journal of the American Chem...· 0 citations
Innovation of sustainable and efficient catalytic systems for controlled aerobic oxidation of alcohols remains a fundamental challenge in green chemistry. Here, we report a phenothiazine‐functionalized covalent organic cage (
P
2
D
3
R
) as a robust heterogeneous platform for photocatalytic dehydrogenat...
S. Pratibha, Neha Gautam, Pallab Bhandari et al.· Annalen der Pharmacie· 0 citations
Metal-catalyzed thermodynamic difference in the stepwise decarboxylative coupling of carboxylic acids on metal surfaces is reported. Our study reveals that the decarboxylative coupling includes three steps: deprotonation, decarboxylation, and C–C coupling. Furthermore, it exhibits a strong underlying-metal-substrate...
Chun-Long Wu, Hao-Yu Wei, Pei-Chao Wang et al.· Journal of the American Chem...· 0 citations
Electrocatalytic nitrate reduction is often framed in terms of metal identity, yet the decisive factor governing reactivity remains the local coordination environment in which that metal is embedded. Here, we demonstrate that a covalent organic framework (COF) can be engineered to encode a hydroxyl–ligand cooperative...
