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Expansion of the synthetic chemists’ toolbox is currently a topic of great interest, with successes providing access to novel compounds and more efficient routes towards new and known pharmaceuticals and agrochemicals. In this context, the development and application of first-row transition metal-catalysed C–H functionalisation protocols is seen as a key opportunity. This perspective provides a brief background of the discovery and application of high-valent cobalt-catalysis in C–H functionalisation, before detailing examples of recent advances in this field using the powerful [Cp*Co(CO)I2] catalysts for both terminal couplings and heterocycle formation. Finally, a discussion on the detection and isolation of elusive reactive intermediates in high-valent cobalt-catalysed C–H functionalisation, shedding light on how these catalyst systems operate, will be provided.

Graphical abstract: Recent advances using [Cp*Co(CO)I2] catalysts as a powerful tool for C–H functionalisation

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