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Pseudokinases are non-canonical protein-kinase-like proteins deficient in kinase activity, few of which have enzymatic activity that differs from phosphorylation. Now a pseudokinase-enabled cyclization activity for the biosynthesis of ribosomally synthesized and post-translationally modified peptides has been observed. Here pseudokinases can catalyse a Michael addition for (ene)thioether crosslinking through a sandwich-like substrate-assisted process.

The hydroheteroarylation of internal alkynes with indolizines via Pd and Rh catalysis is reported. This catalyst-controlled three-dimensional divergent protocol produces eight types of diaryl allyl skeleton (through combinations of E/Z and R/S stereochemistry and 1,1-/1,3-substitution patterns).

(Hetero)aryl sulfoximines are useful bioisosteres of (hetero)aryl sulfones in medicinal chemistry as they have improved aqueous solubility and metabolic stability. Here, the authors report a synthesis of (hetero)aryl sulfoximines via copper-catalysed coupling of (hetero)aryl iodides and sulfenamides.

Tetrasubstituted olefins have been explored as chemical synthons and can sometime have useful photophysical properties, but are sometimes difficult to synthesize with high selectivity in mild conditions. Here the authors present a method to make tetrasubstituted olefins via dual photo- and nickel catalysis, without the need for an inert atmosphere.

Common aromatic rings, such as anilines, arylboronic acids and aryl halides, can be opened up and converted to alkenyl nitriles through carbon–carbon bond cleavage using a copper catalyst.

C-C bond scission of unstrained cycloketones with high regioselectivity is a challenging synthetic task. Here, the authors show a facile C-C cleavage of cyclohexanones and cyclopentanones with unusual selectivity under mild conditions with the aid of an in situ formed side-chain aryl radical.

A method for the site-selective C–H borylation of arenes and heteroarenes is described, in which BBr₃ acts as both a reagent and a catalyst.

C=O cleavage of formamides and full transfer of the resulting fragments into final products are highly appealing, particularly in multi-component reactions for the synthesis of structurally complex molecules. Now three-component reactions of diazo compounds with allylic substrates and formamides are presented, giving extensively reorganized products via multi-step relay.

Rearrangement reactions serve as crucial steps in syntheses of biologically active products and also provide intellectual and conceptual curiosities within the broad field of organic chemistry. Here, the authors report an electrophilic selenylation/semipinacol rearrangement of allenols, catalysed by a chiral Lewis base.

The synthesis of constrained 12-membered peptide rings is challenging due to constraints during the linear peptide cyclization. Here the authors present a β-thiolactone framework that enables the synthesis of cyclo-tetrapeptides via direct aminolysis while preventing commonly observed C-terminus epimerization.

Difluorocarbene transfer is mostly limited to reactions that utilize its intrinsic electrophilicity. Now, a controllable palladium-catalysed difluorocarbene transfer reaction is reported that involves nucleophilic and electrophilic palladium difluorocarbene species. The selective reactions between arylboronic acids and the difluorocarbene precursor BrCF₂PO(OEt)₂ give four different products—difluoromethylated and tetrafluoroethylated arenes and their corresponding fluoroalkylated ketones.

Computational analysis of competing sulfur(VI)–fluoride exchange and modular diazotransfer pathways in the reaction between primary amines and fluorosulfuryl azide reveals that diazotransfer is more kinetically and thermodynamically favoured. Predictive models are formulated by combining mechanistic analysis and structure–activity relationship studies, enabling the development of an easy-to-prepare and highly reactive diazotransfer reagent.

Storage of photon entanglement at telecommunication wavelength is an important milestone for the development of the quantum internet. Here, the authors demonstrate storage and retrieval of entangled telecom photons—generated through SWFM in a silicon nitride microring resonator—in an Erbium doped crystal.

Chirality is an intrinsic property in unsymmetric three-dimensional molecular assembly, contributing to the utility of the corresponding process and the resulting scaffolds. Now, on the sulfur(VI) hub, a three-step sequential ligand-exchange method has been established with precise stereocontrol, enabling the enantioselective synthesis of optically active S(VI) functional molecules.

Although several transition-metal carbene complexes have been isolated and used for catalytic carbene transfer reactions, few metal difluorocarbene complexes have been reported. Now, the synthesis, characterization and reactivity of isolable copper(I) difluorocarbene complexes has been reported, which has enabled the development of a copper-catalysed difluorocarbene transfer reaction to access fluorinated compounds from simple chemical feedstocks.

Using synergistic bimetallic catalysis, a general ring expansion strategy has been developed for cross-dimerization between three-membered aza heterocycles and three- and four-membered-ring ketones. This method provides a straightforward and broadly applicable route for the assembly of 3-benzazepinones, dihydropyridinones and uracils, which are versatile units in numerous drugs and biologically active compounds.