New papers on Catalysis & reactions
51 new papers on catalysis & reactions in the last 7 days, within Chemistry & materials. These are the 50 Pipette rates most worth reading, with the main result in the authors' own words.
The best of the week
Energy-Positive Thiosulfate Production Enabled by Coupling Waste Sulfide Oxidation with Oxygen Reduction
Here we develop a galvanic electrochemical-chemical cascade strategy that couples the sulfide oxidation reaction (SOR) with the two-electron oxygen reduction reaction (ORR), enabling sulfide valorization with net positive electrical energy output.
Peer-reviewed journalReal-world useIndustrial-Scale Electrosynthesis of Amino Acids from the Air via a Molecular Ligand-Engineered Bismuth Catalyst
Here, we report a molecular ligand-engineered bismuth catalyst (L-Bi) prepared via in situ electroreduction of bismuth metal–organic frameworks, achieving a record 93% Faradaic efficiency for glycine synthesis from simulated plasma-oxidized air and glyoxylic acid at a current density of 100 mA cm–2.
Peer-reviewed journalBold claims, read criticallyClaims a big stepReal-world useRachel: A general-purpose language model directs and revises retrosynthetic routes
Within Rachel, a general-purpose LLM coordinated successive chemical choices and revised its strategy as earlier decisions reshaped the remaining problems.
PreprintLiquid–Metal-Induced Metal–Support Interactions for CO2 Hydrogenation
Herein, we demonstrate that metals in liquid state can enable MSI on reducible transition-metal oxides at room temperature and down to −41 °C.
Peer-reviewed journalBold claims, read criticallyClaims a big stepReal-world useEfficient hydrogen peroxide synthesis from seawater via Na- and Pb-codoped SnSe under moderate temperature gradient
Here we show a proof-of-concept thermoelectrocatalytic strategy for H2O2 production directly from seawater, driven solely by low-grade waste heat.
Peer-reviewed journalBold claims, read criticallyReal-world useAI-guided high-throughput discovery of iridium- and ruthenium-free palladium-oxide catalysts for durable acidic oxygen evolution
We report an artificial intelligence (AI)-guided, human-supervised closed-loop platform (>90% automation) integrating combinatorial sputter synthesis, high-throughput screening, machine-learning composition-property models, adaptive multi-objective optimization, and context-aware large-language-model reasoning, where lead catalysts advanced to long-term validation in 1 M H2SO4 at 10 mA cm-2.
PreprintBold claims, read criticallyReal-world useStereodivergent telomerization of linear functionalized dienes with amines
Here we report an orthogonal telomerization platform using linear functionalized 1,3-dienes as the substrates, which simultaneously dictates regio-, geometric, diastereo-, and enantioselectivities.
Peer-reviewed journalClaims a big stepBeyond Direct Two-Electron Oxidation: High-Potential Formaldehyde Oxidation on Palladium Still Generates Hydrogen Atoms
Unexpectedly, permeated hydrogen remains detectable over a broad FOR potential window up to 1.5 V vs RHE (reversible hydrogen electrode), demonstrating that high-potential FOR on Pd is not a hydrogen-free oxidation process.
Peer-reviewed journalReal-world useTyrosinase-Catalyzed Tyr–Aniline Coupling Enables Peptide Editing, Macrocyclization, and Phage-Display-Based Selection
Here, we report a tyrosinase-catalyzed tyrosine–aniline coupling platform that enables peptide editing, conjugation, macrocyclization, and phage-display-based ligand discovery within a single reaction manifold.
Peer-reviewed journalIsocyanoalkynes: Leveraging a High-Energy Interstellar Lead for Unique Multi-Bond-Forming Cascades
Described here is a robust, scalable synthesis of substituted isocyanoalkynes bearing aromatic, heterocyclic, and aliphatic substituents, and a structural analysis complemented by computations that identify molecular hot spots.
Peer-reviewed journalBold claims, read criticallyClaims a big stepSynthesis of a Borylborenium Ion via Direct Dehydrocoupling of Two B–H Bonds
Herein, we report that an in situ-generated dihydroborenium ion can readily undergo dehydrocoupling with an intramolecular o-carboranyl moiety to afford a borylborenium ion.
Peer-reviewed journalClaims a big stepSelective C18-Methyl Oxidation of Sclareol via an Engineered P450 Enables the Synthesis of Spiromyrrhene B
Herein, we report a biocatalytic C-H oxidation strategy that leverages an engineered P450BM3 platform for the selective C18-methyl hydroxylation of sclareol.
Peer-reviewed journalUnlocking Sulfurdiimide Reagents as Radical Traps in the Decarboxylative Synthesis of Sulfinamidines
Taking advantage of the wide abundance of commercially available carboxylic acids, we have developed an acridine/copper cocatalyzed decarboxylative addition into sulfurdiimide reagents, to deliver a diverse range of sulfinamidine products.
Peer-reviewed journalStructural evolution-induced strong-coupling in CuRu-Cu2O nanocomposite enables low-overpotential electrocatalytic ammonia synthesis
Here, the authors report CuRu-Cu2O nanocomposites that achieve 95.4% ammonia Faradaic efficiency at 0 V (reversible hydrogen electrode) and operate stably for over 200 h.
Peer-reviewed journalReal-world useChemoselective Intermolecular Cross-Benzoin Reactions Via Pyridinium-Zwitterion Intermediates
These intermediates subsequently react with a variety of aldehydes, enabling cross-benzoin reactions in high yields and chemoselectivities.
Peer-reviewed journalRadical Disconnection Logic Enables Direct Conversion of α-Amino Acids into Differentiated Vicinal Diamines
Here we introduce a radical disconnection strategy that enables the direct conversion of α-amino acids into differentiated vicinal diamines in a single step.
Peer-reviewed journalBold claims, read criticallyEnhanced alkene productivity in methanol-to-hydrocarbons conversion using a secondary catalyst component and hydrogen co-feeds
Among the tested materials, Pd/SiO 2 provides the highest stability enhancement, leading up to 10× higher cumulative productivity of C 3 –C 5 alkenes, and outperforming a bifunctional Pd-loaded zeolite.
Peer-reviewed journalReal-world useSecondary-sphere hydrogen bonding promotes catalytic nitrate reduction at iron
Here we report a bioinspired strategy to enhance nitrate binding and reduction through a network of secondary-sphere hydrogen-bonding interactions within a ligand scaffold.
Peer-reviewed journalReal-world useTower Loop Engineering Converts a Low-Potential Bacterial Laccase into a High-Potential Laccase with Tunable Catalytic Activity
When combined with axial and secondary coordination-sphere mutations, this design elevates the T1Cu reduction potential from 367 mV to 708 mV vs. SHE, converting a low-potential bacterial laccase into a high-potential laccase.
Peer-reviewed journalBold claims, read criticallyReal-world useAmorphous Interface-Confined Acetylene Semireduction under Industrially Relevant Acetylene-Lean Feeds
The optimized system achieves near-unity ethylene selectivity with strongly suppressed parasitic reactions, enabling efficient acetylene removal to below 5 ppm for 310 h.
Peer-reviewed journalReal-world useConcise Total Syntheses of (−)-Ohioensin A, Putative (+)-Ohioensin C, (+)-Myristinins A and B/C, and (+)-Caesalpinflavan A
Herein, we disclose a unified synthetic approach that culminates in the first concise enantioselective total syntheses of (−)-ohioensin A and putative (+)-ohioensin C, as well as the flavonoids (+)-myristinins A and B/C and (+)-caesalpinflavan A. The synthetic strategy hinges on the development of novel methodologies, including a chiral biphenol-catalyzed enantioselective conjugate addition of alkenyl and aryl boronic acids to 2-hydroxynitrostyrenes, a stereodivergent cyclization to procure both cis- or trans-2,4-disubstituted benzodihydropyrans, and an intramolecular deaminative aromatic homolytic substitution.
Peer-reviewed journalBidirectional Alkene-Nucleophile Coupling at a Single Carbon Center Enabled by a Methylene-Bridged Thianthrenium Dication
To overcome this longstanding challenge, we report a bidirectional coupling strategy that assembles alkenes and nucleophiles across an intervening methylene unit.
Peer-reviewed journalBold claims, read criticallyDeoxygenative functionalization of alcohols, ethers, and carbonyl compounds by chromium catalysis
Herein, we report an efficient and general chromium-catalyzed strategy for the deoxygenative functionalization of alcohols, ethers, and carbonyl compounds with a number of electrophiles.
Peer-reviewed journalBold claims, read criticallyEZSolver: Template-Free Prediction of Polar Enzymatic Mechanisms via Bidirectional Flow Matching and Search
Evaluated across diverse enzyme classes, EZSolver achieves a 60.0% accuracy and an 84.6% chemical plausibility rate for the full-mechanism prediction of unseen polar enzymatic reactions.
Peer-reviewed journalBold claims, read criticallyReal-world useStabilizing ruthenium atom layer neighbors through molecular and metal support interactions for water electrolyzers
We present a versatile platform based on atom-layer neighbors, where the proximity of Ru ensembles diversifies adsorption configurations while simultaneously enhancing adsorbate binding through ligand effects.
Peer-reviewed journalBold claims, read criticallyReal-world usePd-Catalyzed Enantioselective [3+3] Annulation of Vinyldiazos with 2-Iodoanilines Enabled by Sadphos
Herein, we report the first Pd-catalyzed asymmetric [3+3] annulation of 2-iodoanilines with vinyldiazo acetic esters.
Peer-reviewed journalIodide-bridged interfacial hydrogen bonds enable ampere-level electrosynthesis of deuterated acetic acid
Here, the authors report an iodide microenvironment engineering strategy to rigidify the H bond network for the efficient dehalogenative deuteration of trichloroacetic acid to acetic acid.
Peer-reviewed journalBold claims, read criticallyMultivariate approach of metal-chiral covalent organic frameworks for leaching-resistant asymmetric transfer hydrogenation
Here, we introduce a modular multivariate approach strategy coupled with post-synthetic metalation to engineer metal-chiral COFs (MCCOFs) with tunable crystallinity, porosity, and stereocontrol.
Peer-reviewed journalReal-world useDivergent ring opening and functionalization of N-alkyl aziridines via boryl radical fragmentation
Here we report a general radical activation mode that directly engages N-alkyl aziridines in ring-opening and divergent functionalization.
Peer-reviewed journalFunctional Group Transpositional Trimolecular Cross-Coupling via Interrupted Homolytic Substitution
Here we introduce a strategy that leverages interrupted homolytic substitution (int-SH2) to enable FGR, specifically redirecting allylamine reactivity toward modular trimolecular cross-coupling via nickel/photoredox dual catalysis.
Peer-reviewed journalReal-world useEmbracing triplet nitrenes for C-to-N replacement of complex bicyclic (hetero)aryl azides
In this work, we report a reaction that productively engages triplet aryl nitrenes for carbon-to-nitrogen replacement on the benzenoid ring of a range of bicyclic heteroarenes, including naphthalenes, anthracene, indoles, benzofurans, benzothiophene, indazoles, and benzisothiazoles.
Peer-reviewed journalBiocatalytic Redox Cascade Enabled Site-Selective Direct β-Alkylation of Cyclopentanones
Herein, we report a highly site-selective direct β-C(sp3)–H alkylation of α-nonacyl-substituted cyclopentanones via photobiocatalysis.
Peer-reviewed journalEnantioselective Defluorinative C(sp2)–H Allylation of Acrylamides Enabled by CpxRh(III) Catalysis
Herein, we report a convergent strategy that merges asymmetric alkenyl C(sp2)–H functionalization with defluorinative coupling, enabling the direct, enantioselective synthesis of fluorinated skipped 1,4-dienes from readily available starting materials.
Peer-reviewed journalLattice distortion strain modulation of twin-defective noble-metal-free high-entropy alloy electrocatalyst for Li−O2 batteries
Here, authors demonstrate that lattice strain induced by large-size Ce doping generates coherent five-fold twinning in noble-metal-free high-entropy alloy nanoparticles, which serve as efficient electrocatalysts for non-aqueous Li–O2 batteries.
Peer-reviewed journalBold claims, read criticallyReal-world useUsing Data Science Tools to Explore Rate Matching in a Nickel-Catalyzed Cross-Electrophile Coupling of Alkyl and Aryl Halides (Cl, Br) with a Tridentate Monoanionic Ligand
We found that productive coupling occurs in a specific rate regime, and the synthetic performance could be predictably modulated by choosing the "matched" halide (either chloride or bromide) for each coupling partner.
Peer-reviewed journalIron-Electrocatalytic MHAT Enables C–F Bond Activation of CF3 Alkenes: Access to Stable Keto and Enol Isosteres
Using an iron porphyrin catalyst and urea as the proton source, this protocol enables the selective C–F bond activation of CF3 alkenes to furnish gem-difluoroalkenes with a broad substrate scope under mild conditions.
Peer-reviewed journalBold claims, read criticallyReal-world useElectrochemical Upgrading of Lignin-Derived Phenolics via Vanadium Redox-Mediated Decoupling
Here, using phenol as a model, we report a redox-mediated strategy that spatially decouples electrode reactions from catalytic hydrogenation steps via a V3+/V2+ shuttle, effectively bypassing the interfacial diffusion barrier.
Peer-reviewed journalBold claims, read criticallyReal-world useUnveiling full mechanistic picture of Mo-catalysed nitrogen fixation driven by SmI2–H2O system
Here we show a full catalytic mechanism by combining mechanistic experiments and theoretical analyses.
Peer-reviewed journalCatalytic C(sp2)–F Bond Gallylation via Dynamic Ni–Ga Cooperativity
Here, we report an unsupported Ni–Ga heterometallic system for the conversion of C(sp2)–F into C(sp2)–Ga bonds, capable of dynamically switching between bimetallic and trimetallic catalytic regimes to achieve key steps along the catalytic cycle.
Peer-reviewed journalWater-Enabled Conversion of NO and CO to NH3 over CuO x Clusters via Hydrolysis of Surface –NCO Intermediates
This work highlights that a simple, earth-abundant Cu catalyst enabled the efficient and cost-effective synthesis of NH3 from air pollutants of NO and CO under mild conditions, underscoring a sustainable strategy that simultaneously addresses pollution abatement and resource recovery.
Peer-reviewed journalBold claims, read criticallyReal-world useDecoding CO2 Adsorption Modes and CO Yield Variation on TM–N4 Single-Atom Catalysts via Constant-Potential Computation and Machine-Learning Investigation
Thus, this work establishes Utrans as a novel predictive parameter for CO yield performance and offers valuable guidance for the design of advanced SACs in future studies.
Peer-reviewed journalMultiplicative Stereocontrol in the Light-Driven Deracemization of Benzylic Nitriles
Here we report a light-driven deracemization of benzylic nitriles with up to 99% yield and 98% ee enabled by cooperative photoredox and chiral phosphate catalysis that achieves high overall enantioselectivity through the combination of two moderately stereoselective steps.
Peer-reviewed journalUnnatural α-amino acid synthesis enabled by nickel-catalysed enantioselective hydrocarbamoylation of enamides via C‒H functionalisation
Herein, we report a straightforward and efficient method for the assembly of structurally diverse enantioenriched α-amino acid derivatives from readily accessible enamides and N,N-dimethylformamide (DMF) by merging nickel hydride catalysis and hydrogen atom transfer (HAT).
Peer-reviewed journalReal-world useOn-Surface Heptagon Contraction Enables Rearrangement Driven Selective C–C Coupling
Here, we report a rearrangement-driven coupling reaction on Au(111) in which a heptagon undergoes a [7 → 6 + 1] contraction before intermolecular bond formation, thereby generating reactive termini for subsequent covalent growth.
Peer-reviewed journal( N -Hydroxy)amide-Mediated Rapid Head-to-Tail Cyclization of Unprotected Peptides in Water
Here, we report a (N-hydroxy)amide-mediated rapid head-to-tail cyclization of unprotected aminoacyl (N-hydroxy)peptide hydrazides with different lengths and sequences in water.
Peer-reviewed journalStructural Basis of Cyclized C17 Precursor Recognition and Product Formation in Chlororaphen and Grimophan Biosynthesis
Here, we report high-resolution crystal structures of two bacterial C17 class I TCs, Pc-ChloS and Vb-GriS, including a complex with a substrate surrogate that defines recognition of the cyclized precursor α-prechlororaphen pyrophosphate (α-PCPP).
Peer-reviewed journalFlavin Takes Charge: CdS Nanorods Drive Light-To-Dark Electron Flow
Here, we show that colloidal CdS nanorods (NRs) drive efficient photoreduction of riboflavin (Rf) and flavin mononucleotide (FMN) while suppressing competing photodegradation pathways.
Peer-reviewed journalLigand-Shell-Enabled Silver Catalysis on Gold Nanoclusters for the Straightforward Synthesis of β-Naphthol Ethers from Alkynes
Herein, we present a rare example of employing chloride-containing gold nanoclusters to form Au–Cl–Ag reactive intermediates within protective ligand shells, enabling the isomerization/cyclization of alkynes to directly construct naphthalene rings.
Peer-reviewed journalDiastereodivergent Access to cis , cis - and cis , trans -Angular Triquinanes: Total Synthesis of (±)-Arnicenone
Herein, we report a diastereodivergent strategy for stereocontrolled access to both cis,trans- and cis,cis-angular triquinanes from common allene precursors.
Peer-reviewed journalA Redox-Mediated Negative Feedback Loop Based on Tetrazine-Thiol Exchange
Here, we designed a negative feedback loop based on thiol-tetrazine exchange (TeTEx).
Peer-reviewed journalBold claims, read critically