Site-predictable and chemoselective C–H bond functionalization reactions offer synthetically powerful strategies for the step-economic diversification of both feedstock and fine chemicals. Many transition-metal-catalyzed methods have emerged for the selective activation and functionalization of C–H bonds. However, challenges of regio- and chemoselectivity have emerged with application to highly complex molecules bearing significant functional group density and diversity. As molecular complexity increases within molecular structures the risks of catalyst intolerance and limited applicability grow with the number of functional groups and potentially Lewis basic heteroatoms. Given the abundance of C–H bonds within highly complex and already diversified molecules such as pharmaceuticals, natural products, and materials, design and selection of reaction conditions and tolerant catalysts has proved critical for successful direct functionalization. As such, innovations within transition-metal-catalyzed C–H bond functionalization for the direct formation of carbon–carbon bonds have been discovered and developed to overcome these challenges and limitations. This review highlights progress made for the direct metal-catalyzed C–C bond forming reactions including alkylation, methylation, arylation, and olefination of C–H bonds within complex targets.

We discuss recent advances in the applications of cycloruthenated complexes in organic synthesis, comprising C–H activation, chiral-at-metal catalysis, Z-selective olefin metathesis, transfer hydrogenation, enantioselective cyclopropanations and cycloadditions.

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A ruthenium-catalysed C–H arylation procedure that utilises a range of green solvents in place of the undesirable solvent NMP is presented. Examples of fast reaction time, low catalyst loading and large-scale reactivity are also shown.