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Various rhodium-catalyzed double C–H activations are reviewed. These powerful strategies have been developed to construct C–C bonds, which might be widely embedded in complex aza-fused heterocycles, polycyclic skeletons and heterocyclic scaffolds. In particular, rhodium(III) catalysis shows good selectivity and reactivity to functionalize the C–H bond, generating reactive organometallic intermediates in most of the coupling reactions. Generally, intermolecular, intramolecular and multi-component coupling reactions via double C–H activations with or without heteroatom-assisted chelation are discussed in this review.

Graphical abstract: Rhodium-catalyzed C–C coupling reactions via double C–H activation

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