Dual-Catalysed Intermolecular Reductive Coupling of Dienes and Ketones.

We report a mild, catalytic method for the intermolecular reductive coupling of feedstock dienes and styrenes with ketones. Our conditions allow concomitant formation of a cobalt hydride species and single-electron reduction of ketones. Subsequent selective hydrogen-atom transfer from the cobalt hydride generates an allylic radical which can selectively couple with the persistent radical-anion of the ketone. This radical-radical coupling negates unfavourable steric interactions of ionic pathways and avoids the unstable alkoxy radical of previous radical olefin-carbonyl couplings, which were limited, as a result, to aldehydes. Applications of this novel and straightforward approach include the efficient synthesis of drug molecules, key intermediates in drug synthesis and site-selective late-stage functionalisation.

Photo- and Electrochemical Cobalt Catalysed Hydrogen Atom Transfer for the Hydrofunctionalisation of Alkenes.

Catalytic hydrogen atom transfer from metal-hydrides to alkenes allows feedstock olefins to be used as alkyl radical precursors. The chemoselectivity of this process makes it an attractive synthetic tool and as such it has been regularly used in synthesis of complex molecules. However, onwards reactivity is limited by compatibility with the conditions which form the key metal-hydride species. Now, through the merger with photocatalysis or electrochemistry, milder methods are emerging which can unlock entirely new reactivity and offer perspectives on expanding these methods in unprecedented directions. This review outlines the most recent developments in electro- and photochemical cobalt catalysed methods and offers suggestions on the future outlook.

Dual Photoredox/Cobaloxime Catalysis for Cross-Dehydrogenative α-Heteroarylation of Amines.

We report a dual-catalytic platform for the cross-dehydrogenative-coupling between (benzo-)thiazoles and amines which combines low loadings of an iridium photoredox catalyst and a cobaloxime catalyst under blue light irradiation. This transformation occurs without stoichiometric oxidants, giving products in moderate to excellent yields. DFT calculations support the key role of Co(II) for rearomatization of the radical-addition intermediate to generate the product.