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Discovering hydrogen evolution reaction (HER) catalysts is challenging yet vital for energy and potentially synthesis. Here alkali metal–cobalt Salen systems with high HER activity is developed and is repurposed for C–H functionalization.

Metal–sulfur motifs are commonly found in enzymatic active sites and heterogeneous catalysis, but they remain underexplored in porous solids. Now, sulfur-based ligands have been incorporated into metal–organic frameworks through post-synthetic modifications. The resulting sulfide MOFs exhibit enhanced catalytic performance in the selective hydrogenation of nitroarenes compared with their parent MOFs containing terminal or bridging chloride and hydroxyl groups.

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).

Converting plastic waste into single-atom catalysts (SACs) provides both a sustainable approach to waste management and a source of valuable catalytic materials. Here, the authors present a straightforward, scalable method to upcycle plastic waste into diverse porous SACs and showcase their outstanding performance across multiple catalytic reactions.

Iron carbide catalysts—especially the Fe₇C₃; phase—show great promise for efficient CO₂ hydrogenation to olefins. Here, the authors report the first stable, nearly pure Fe₇C₃ catalyst for CO₂-to-olefins conversion, overturning conventional models that posit the necessity of Fe₅C₂–Fe₃O₄ coexistence.

Polysubstituted arenes are ubiquitous structural cores in natural products and drugs but their synthesis through programmable arene modification remains a challenge. Now, a palladium- and norbornene-catalysed Catellani-type reaction of aryl ketones, through successive acylation and deacylation, allows the synthesis of polysubstituted arenes.

C-oligosaccharides are found in natural products and drug molecules, but their synthesis is challenging. Here, the authors report a strategy for the stereoselective and efficient synthesis of Coligosaccharides via palladium-catalyzed nondirected C1–H glycosylation/C2-alkenylation, cyanation, and alkynylation of 2-iodoglycals with glycosyl chloride donors.

Xu et al. present RXNGraphormer, a pre-trained model that learns bond transformation patterns from over 13 million reactions, achieving state-of-the-art accuracy in reaction performance prediction and synthesis planning.

The oxidative intermolecular amination of C-H bonds represents a straightforward method to construct aliphatic allylic amines. However, the utilization of widely available internal alkenes remains a synthetic challenge. Here, the authors present a regioselective Cu-catalyzed oxidative allylic C-H amination of internal olefins with azodiformates.

Heavier group 14 carbene analogue display remarkable capability for small molecule activation but their application in redox catalysis remains elusive. Here, the authors report the synthesis and isolation of a stannylene with carbodiphosphorane ligand and characterize its catalytic activity in the hydrodefluorination reaction of fluoroarenes.

High-spin Fe(IV) = O sites efficiently activate methane but are challenging to synthesize. This study develops dual Fe(II) sites on FeS₂, generating high-spin Fe(IV) = O from O₂, achieving superior methane-to-methanol conversion under mild conditions.

The implementation of asymmetric Heck/cross coupling cascades of highly flexible haloalkene substrates remains a challenging and long-standing goal. Here the authors report an asymmetric domino Heck/Tsuji−Trost reaction of flexible vinylic halides with 1,3-dienes enabled by palladium catalysis.

Lignin refining continues to face major challenges in achieving selective depolymerization and breaking resistant C–C bonds. In this work, the authors design a robust atomically dispersed Cu/Ni-SA@HNC catalyst that enables highly selective hydrogenolysis of lignin and model compounds through an unconventional pathway involving preferential Cα–Cβ bond cleavage in β-O-4 linkages.

Selective CO₂ hydrogenation to methanol under mild conditions remains challenging. Here, sulfur-bridged Mo binuclear sites on covalent triazine frameworks enable efficient room-temperature conversion via cooperative CO₂ activation and H₂ splitting.

CO oxidation catalysts face a tradeoff between high activity and stability due to oxidation-induced deactivation. By trapping Pt clusters at stepped CeO₂ pockets, this work circumvents the stability-activity dilemma.

Pd catalysts are promising for methane-to-methanol conversion, but structure–performance links remain unclear. This study uses facet-controlled Pd nanocrystals, revealing {111}-facets enhance methanol yield via optimal intermediate adsorption.

Simultaneous oxidation of soot and CH₄ is challenging in dual-fuel engines. This study introduces a Ru-Pd/3D macromesoporous Ce-Zr oxide catalyst, significantly enhancing oxidation via cooperative Ru (NO activation) and Pd (CH₄ activation) sites.

Achieving selective propylene epoxidation with molecular oxygen is a highly sought-after yet difficult objective. Here, the authors present a novel approach involving ligand protection and selective facet etching to synthesize internally hollow Cu₂O nanoframes, which exhibit outstanding catalytic activity for the reaction.

Developing Ru-intermetallic catalysts for mild ammonia synthesis faces structural complexity. Here, machine learning identified Sc_1/8Nd_7/8Ru₂, optimizing Ru–N bonding and orbital hybridization, enhancing catalytic activity under mild conditions.

Single-atom catalysts (SACs) face synthesis and structural control challenges. Here a scalable NaCl-template strategy is developed to produce diverse SACs with tailored coordination, enhancing catalytic performance for environmental and energy uses.

Catalytic asymmetric click reactions of azides and alkynes for chiral triazole synthesis remains a challenge, due to the limited catalytic systems and substrate scope. Herein, the authors report the enantioselective azidation/click cascade reaction of N-propargyl-β-ketoamides via copper catalysis, affording a variety of chiral 1,2,3-triazoles.

Angular tricyclic and polycyclic skeletons feature typical cores in an intriguing type of natural products. Herein, the authors report Lewis acids catalyzed dearomative (3 + 2) cycloadditions of donor-acceptor cyclopropanes with benzene ring for the synthesis of diverse angular tricyclic and polycyclic carbocycles.

Developing skeletal editing tools, especially to realize the single-atom transmutation in a ring system without altering the ring size is challenging. Here, the authors introduce a skeletal editing strategy that enables polycyclic arenols to be readily converted into N-heteroarenes through carbon–nitrogen transmutation.

In this work, an acceptor-donor-acceptor type fluorobenzene-linked perylene diimide photocatalyst was used for selective conversion of CO₂ to C₂H₆ in pure water.

Atomic-level catalyst design faces challenges in methane activation and selective C–C coupling. Here, Ru atoms anchored on graphdiyne enhance methane oxidation, achieving high selectivity and yield for valuable C₂ liquid oxygenates.

Saturated three-dimensional carbocycles have gained increasing prominence in synthetic and medicinal chemistry. Here, the authors present facile access to a variety of bicyclo[2.1.1]hexanes via a stepwise two-electron formal (3 + 2) cycloaddition between silyl enol ethers and bicyclo[1.1.0]butanes under Lewis acid catalysis.

Direct CO₂ conversion into high-value organic products faces significant selectivity challenges. This work presents a FeCo carbide-based tandem catalyst enabling high-efficiency, stable production of C2+ alcohols.

Efficient oxygen activation limits oxidative catalysis. Here, incorporating single-atom Zr into CeO₂-supported Pt catalysts creates Zr₁–O–Pt₁ structures, significantly enhancing catalytic performance via boosted surface and chemisorbed oxygen activation.

ZeoBind is developed for high-throughput molecule screening in zeolite synthesis. Here 2.3 million organic structure-directing agents are enumerated and predictive models for binding affinity are developed; the screening is experimentally validated for two zeolites.

Catalyst reconstruction via reaction environment is promising but complex. Here, Ni-doped Ce-based nanorods undergo regioselective reconstruction into dual-active carburized Ni clusters and frustrated Lewis pairs, enhancing CO₂ conversion efficiency.

Creating highly active materials that effectively harness solar spectra is essential for photocatalysis, though challenging. Here the authors introduce a novel donor-acceptor covalent organic framework with a broad absorption range of 200 nm to 900 nm, achieving efficient artificial photocatalytic amine coupling.

The lack of efficient and diverse synthesis strategy has hindered the study of perifused cycles. Here, the authors report a metal-catalyzed cascade electrocyclization to access 5,6,7-perifused cycles, and demonstrated the versatility of this protocol in the late-stage modification of pharmaceuticals.

The development of catalysts for practical asymmetric hydrogenation of ketones remains an important goal of synthetic organic chemistry. Here, an anionic iridium catalyst with excellent activity is reported and used in a hundred-kilogram-scale reduction as part of a route to chiral nicotine.

Allylic substitution reaction of alkenes has been well-developed, but it has limitations, partly due to the intrinsic predilection for an inner-sphere mechanism. Herein, the authors present an outer-sphere mechanism in Rh-catalyzed allylic substitution reaction of simple alkenes using gem-difluorinated cyclopropanes as allyl surrogates.

Exploitation of noncovalent interactions has received much attention for the design of metal catalysts. However, because of the weak nature, CH-π interactions have been less utilized for the control of organic reactions. Here, the authors report that the CH-π interaction can be used to kinetically accelerate catalytic C-H activation of arenes.

Templated synthesis is a valuable method for the preparation of oligomers but requires stoichiometric amounts of the template. Here a catalytic macrocyclic template is reported that promotes the oligomerization of a small-molecule substrate and controls its length. The length of the oligomer correlates with the dimensions of the template.

The photochemical properties of Electron Donor-Acceptor (EDA) complexes present exciting opportunities, but often require an inert atmosphere to maintain high efficiency. Here, the authors develop a photocatalytic system through rational design, which overcomes the oxygen-sensitive limitation of traditional EDA photocatalytic systems.

A topochemical oxidation process is developed to exfoliate metal oxyhydroxides, in which active oxygen species and alkali cations modulate interlayer repulsion. The resulting Cs⁺-CoFeOOH nanosheets demonstrate exceptional electrocatalytic performance for the oxygen evolution reaction.

Three-component, iron-based catalytic transformations offer a promising and sustainable approach to building complex molecules in a single step. This Review highlights advances and ongoing challenges in the development of iron-catalysed difunctionalization of alkenes. Mechanistic insights that enhance our understanding and guide the development of new transformations are discussed.

Homoenolates and their higher homologs have much potential, albeit largely unrealized, in transition metal catalysis. Here, the authors report the nickel-catalyzed generation of homoenolates, and their higher homologs, via decarbonylation of cyclic anhydrides, which then undergo cross-coupling with alkyl bromides.

Acid chloride formation is generally limited to the chlorination of carboxylic acids. Here, the authors report a palladium-catalyzed regiodivergent hydrochlorocarbonylation of alkenes for the synthesis of various alkyl acid chlorides.

Despite the growing importance of fluorinated organic compounds introduction of fluorine into organic molecules is still challenging. Here, the authors present the development of palladium and phosphine synergistic redox catalysis of fluorocarbonylation of potassium aryl/alkyl trifluoroborate.

Difluorocarbene, an important reactive intermediate in organic synthesis, exhibits intriguing properties and synthetic versatility. Herein, the authors report a copper catalyzed multicomponent reaction of amine, aldehyde and BrCF₂CO₂K via copper-difluorocarbene intermediate for the synthesis of multifunctional α-aminoamide derivatives.

Ring-opening reactions of bicyclo[1.1.0]butanes (BCBs) provide a reliable platform for synthesizing functionalized cyclobutanes, Herein, the authors report a catalyst-controlled, regiodivergent α- and β‘-selective hydrophosphination of acyl BCBs.

Asymmetric intermolecular hydroamination of alkenes is a challenging process, potentially leading to useful chiral amines. Here, the authors report unsymmetric NNN tridentate ligands promoting the cobalt-catalyzed radical hydroamination of alkenes via hydrogen atom transfer, also in an asymmetric fashion.

One strategy to address multidrug resistance in cancer is the development of modular methods to access bioactive scaffolds. Here, the authors report a Rh(III)-catalyzed carboxylic acid-directed C(sp²)−H allylation and apply it to the modular synthesis of (Z)-allylic macrolides which enhance antitumoral drug activity.

The development of 3d-metal-catalyzed β-C–H bond activation via 4-membered metallacycles remains an elusive challenge. Here, the authors report a Ni-Al bimetal-catalyzed β-C(sp3)–H bond activation of formamides via 4-membered nickelacycles.

The difunctionalization of diazo compounds, traditionally with one nucleophile and one electrophile, is a powerful strategy. Here, the authors develop a path of electrochemical oxidative difunctionalization of diazo compounds with two different nucleophiles.

Selective CO₂-to-liquid conversion remains a major challenge due to inertness of CO₂. This work designs Pd nanoneedles with bent Pd–Pd bonds, enabling >99% selective formic acid production under mild conditions by enhancing CO₂ activation.