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Biaryls are privileged structural motif used in the discovery and design of therapeutics with high affinity and specificity for a broad range of protein targets. Herein, the authors develop a robust strategy for para-C–H arylation of arenes with a range of (het)aryl iodides, including bioactive molecules.

Site-selective C–H functionalization still faces some challenges, such as the introduction and removal of an appropriate directing group. Here, the authors introduce a temporary directing group for selective meta-C–H functionalization of 2-arylbenzaldehydes via reversible imine formation.

Electrophilic acylation of arenes is largely limited to electron rich systems, non-polar medium and often displays moderate selectivity. Here, the authors show a directed para-selective ketonisation of arenes, overriding electronic bias and structural congestion, and apply it to the synthesis of bioactive compounds.

Transition-metal-catalyzed C–H arylations are an effective tool for the construction of biaryl motifs in an efficient and selective manner. Here the authors provide an overview of the state-of-the-art of the field and perspectives on emerging directions toward increased sustainability.

Enantioenriched alkyl–alkyl bonds are produced from abundant alkenes in one step via Ni-catalysed asymmetric cross-hydrodimerization. This technique overcomes the reactivity and selectivity challenges associated with coupling between two similar nucleophiles.

The direct cross-electrophile coupling of (hetero)aryl halides and pseudohalides is challenging. Now this reaction is facilitated by a visible light-induced palladium catalytic system that differentiates the reactants on the basis of the bond dissociation enthalpy affording unsymmetrical (hetero)biaryls.

Biocatalytic methods for the synthesis of isoindolones, via C–H activation, have remained elusive. Now, an enantiodivergent artificial-metalloenzyme-catalysed method for the synthesis of chiral isoindolones is reported, using a streptavidin–biotin–Rh(III) catalyst system. Crystallographic analysis reveals the key residues that control stereoselectivity in streptavidin.

Regioselective distal C-H functionalization of nitroarenes by overriding proximal C-H activation has remained an unsolved challenge. Herein, the authors present a palladium-catalyzed meta-C-H alkenylation of nitroarene substrate, achieved through leveraging the noncovalent hydrogen bonding interactions.

Dehydrogenation chemistry can be used to generate units of unsaturation that can later be functionalized, as well as create aromaticity, which fundamentally alters the properties of molecules. Here the authors show methodologies to create multiple types of units of unsaturation from aliphatic cyclic carboxylic acids via palladium catalyzed decarboxylative multifold C–H activation.

Contrary to photocatalysis, the use of photochemical energy solely to initiate reactions is underexplored. Here, the authors demonstrate light initiated synthesis of functionalized organosilanols, silanediols, and polymeric siloxanol under ambient reaction conditions.

An efficient CO₂-to-CO conversion can provide a perfect leeway for transforming waste CO₂ into industrially viable CO. Here, the authors report a bio-inspired copper based synthetic catalyst that can convert CO₂ to CO with minimal energy penalty in both organic and aqueous media.

Bicyclic lactones are valuable motifs for the synthesis of natural products and bioactive molecules. Now, a palladium-catalysed protocol has been developed to access unsaturated bicyclic lactones in one step from corresponding carboxylic acids. The method demonstrates reverse site selectivity for C(sp³)–H activation to form diverse bicyclic cores.

Transient directing groups enable selective metal-catalysed C–H functionalization reactions to give diverse products. These directing groups form and dissociate in situ, such that their use is an efficient route to complex organics, examples of which are summarized in this Review.