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The precise manipulation of unfunctionalized hydrocarbons remains a fundamental challenge in chemical synthesis and catalysis. Here an organocatalytic asymmetric hydroxylation of bicyclobutanes with alcohols is disclosed, enabling efficient access to tertiary cyclopropylcarbinyl ethers with high enantioselectivity (up to 98:2 e.r.).

Thiophene S,S-dioxides are excellent substrates for cycloaddition reactions, but underused in target-oriented synthesis. Here the authors show how these heterocycles enable the asymmetric synthesis of tricyclic indolines, as well as the collective synthesis of the iconic Strychnos alkaloids. Computational studies rationalize the source of asymmetry and reveal a spontaneous SO₂ extrusion pathway.

Complex reaction networks can reach out-of-equilibrium steady states with multiple product-determining steps. Now it has been shown that a four-component photochemical network enables selective GlcNAc-to-GalNAc epimerization. Boronic ester co-catalysis tunes hydrogen-atom abstraction and donation to enhance site selectivity and diastereoselectivity, illustrating kinetic network control for selective catalysis.

Cultivation of tropical soil microorganisms combined with physiological experiments and bioinformatics analyses identify a family of clade III lactonase-type nitrous oxide reductases with low sequence identity but high 3D structural similarity to known nitrous oxide reductases.

Benzofurazan, a cyclic heterocycle, can form open-chain metal carbene species in the presence of suitable catalysts. Here the authors show divergent reactivity when using gold(III) and platinum(II) catalysts, and perform computational and experimental mechanistic studies to explain the differing reactivity

Methods to allow access to all isomers of a product are both valuable and challenging to achieve. Here the authors report a catalytic system comprised of an N-heterocyclic carbene and an iridium complex, and show that it can be used for the asymmetric, diastereodivergent synthesis of γ-butyrolactones.

Catalytic asymmetric synthesis of stable, acyclic N-stereogenic amines by the addition of enol silanes to nitronium ions that ion pair to a confined chiral anion is described.

Photochemical nitrene transfer offers a green avenue for heterocyclic syntheses. Here, the authors developed a metal-free, visible light-mediated cascade reaction for the preparation of azepinone derivatives.

1,3-Disubstituted bicyclo[1.1.1]pentanes are linear bioisosteres for para-substituted benzene rings; however, the lack of practical reagents for the introduction of bicyclopentane currently impedes their application, especially in drug development. Now, stable thianthrenium-based bicyclopentane reagents are reported and their use in O-, N- and C-alkylation reactions demonstrated.

Ring-expanding carbon-atom insertion reactions are currently limited to the installation of few functional groups. Now researchers show the use of a radical carbyne precursor for the insertion of carbon atoms bearing varied functional groups to access 2-substituted naphthalenes from indene.

Azoxy products have rarely been synthesized using enzyme catalysts. Herein, the authors report that fungal unspecific peroxygenases are promising catalysts for synthesizing azoxy products from simple aniline starting materials.

This work challenges the view of nucleation governing halide perovskite grain morphology, showing that most additives act post-nucleation by boosting ion mobility across grain boundaries, triggering grain coarsening, similar to post-processing effects.

Hydrogen oxidation in alkaline media is limited by slow reaction kinetics. Here, the authors develop a family of bimetallic catalysts by theoretical analysis and reveal that RuIr achieves superior activity and durability through synergistic adsorption of hydrogen and hydroxyl intermediates.

Gold redox catalysis is an attractive synthetic method but challenging due to the high redox potential of Au(I)/Au(III). Now, a bidentate N-ligand-assisted gold redox catalysis using H₂O₂ as oxidant has been developed. It can be applied to various coupling reactions, including C(sp)–C(sp) cross-coupling, alkynylative cyclization and bicyclization coupling.

Palladium-catalysed allylic substitution is a widely used method in organic synthesis, although it requires prefunctionalized starting materials or stoichiometric oxidants. Here the authors report a radical route to form π-allylpalladium complexes, and develop a 1,4-aminoalkylation of dienes under redox-neutral conditions.

How cells respond to replication-derived DNA damage that is carried over into mitosis is not well understood. Here, the authors show that CIP2A with TOPBP1 mediates the mitotic recruitment of the SLX4/MUS81/XPF nuclease complex to replication stress-induced DNA lesions to maintain genome integrity.

GTPase-activating proteins (GAPs) often contain regulatory PH domains. In this work, Soubias et al, using an integrated structure-function approach, discovered a mechanism where a GAP PH domain binds directly to a GTPase to induce allosteric changes facilitating GTP hydrolysis.

Regrowth of lost enamel in tooth decay and sensitivity is a major obstacle to overcome. Here, the authors report on a protein-based material that mimics features of natural enamel formation, allowing for epitaxial growth of apatite nanocrystals to restore enamel structure and function.

The synthesis, structure and reactivity of room-temperature-stable [Cp(C₆F₅)₅]⁺[Sb₃F₁₆]⁻ is presented. Coordination of the cyclopentadienyl cation by [Sb₃F₁₆]⁻ or C₆F₆ stabilizes the antiaromatic singlet state in the solid state. Calculated hydride and fluoride ion affinities of the [Cp(C₆F₅)₅]⁺ cation are higher than those of the tritylium cation [C(C₆F₅)₃]⁺.

STM investigations and first principles calculations provide an understanding of the microscopic mechanism behind the mobility of N-heterocyclic carbenes (NHCs) on gold surfaces. Now, it is shown that a ballbot-type motion allows the formation of self-assembled monolayers due to the NHC extracting a gold atom from the surface, leading to a ligated gold adatom.

Ketyl radicals can be used in a range of reactions, but their generation often requires harsh conditions and a large excess of reductants. Now, a multicomponent, palladium-photocatalysed reaction between aldehydes, 1,3-butadiene and N, S, O and C nucleophiles to build architecturally complex homoallylic alcohols is reported wherein ketyl-type radicals are generated under mild conditions.

Hydrocarbons are challenging to functionalize. Here, the authors present an electrochemical oxo-functionalization of cyclic alkanes and alkenes to ketones and dicarboxylic acids via mediating nitrate-based supporting electrolyte and molecular oxygen.

Understanding nanoparticle catalysis is limited by complex structure–activity links. This study reveals that Pt corner sites on 1–1.5 nm particles drive activity via electronic effects, offering a rare quantitative insight into water gas shift catalytic performance.

The ability to rapidly functionalize polymers is vital for application development. Here, a method for the introduction of masked ketenes into monomers for both ring-opening metathesis and radical-type polymerizations is described. These ketenes — a group previously underexploited in polymer chemistry — allow both crosslinking and post-polymerization functionalization of the polymers.

Heteroatom-substituted C(sp³)-rich polycyclic hydrocarbon rings, isosteric to heterocyclic rings, are not common due to the challenging synthesis. Now a photoredox-catalysed strategy to insert amidyl radicals into bicyclo[1.1.0]butanes is presented, providing direct access to 2-oxa-4-azabicyclo[3.1.1]hept-3-enes.

Phosphatidylserine-exposing extracellular vesicles in body fluids can inhibit infection of viruses that use viral apoptotic mimicry for infection, but not viruses that use other entry mechanisms.

Evaluation of foraminiferal test dissolution by Computed Tomography scanner provided deep seawater carbonate ion concentration at the Southern Ocean. Quantitative data highlighted the reconfiguration of glacial to deglacial carbon storage followed by oceanic-atmospheric CO2 transfer.

The reversible N–H activation and catalytic transformations of ammonia are a challenge. Now, a hidden frustrated Lewis pair is shown to activate non-aqueous ammonia thermoneutrally and split the N–H bond reversibly at ambient temperature. The N–H-activated ammonia was also utilized as an atom-economical nitrogen source for catalytic NH₃ transfer reactions.

Hydrogenation is one of the most common catalytic processes on both laboratory and industrial scales, and typically is carried out with a noble metal catalyst. Here, the authors show that alkaline earth metal amides are capable of hydrogenating imines under mild conditions.

Photoswitches are useful in a range of applications, with designing molecules with desirable properties remaining a key challenge. Here, the authors report hemiphosphoindigo chromophores enabling chiroptical and in-water photoswitching with high thermal stabilities, fatigue resistance and isomer enrichment in the photostationary state.

A strain-release approach, realized by visible-light-mediated triplet energy transfer catalysis, enabled an intermolecular [2π+2σ]-photocycloaddition.

Mononuclear complexes of certain lanthanide ions are known to have large magnetization reversal barriers caused by strong spin–orbit coupling. Now, careful tuning of the ligand field of a transition metal complex has engendered a comparable spin-reversal barrier — and in turn magnetic blocking at 4.5 K.

AfCycDesign: Cyclic offset to the relative positional encoding in AlphaFold2 enables accurate structure prediction, sequence redesign, and de novo hallucination of cyclic peptide monomers and binders.

Ammonia oxidizing archaea and Nitrospinae are the main known nitrifiers in the ocean, but the much greater abundance of the former is puzzling. Here, the authors show that differences in mortality, rather than thermodynamics, cell size or biomass yield, explain the discrepancy, without the need to invoke yet undiscovered, abundant nitrite oxidizers.

Milling and grinding, long used to alter the chemical and physical properties of materials, have recently garnered interest as alternatives to traditional solution-based syntheses — but these reactions remain difficult to monitor. High-energy synchrotron X-ray radiation has now enabled the in situ observation, in real time, of solid-state transformations occurring during the mechanochemical syntheses of metal–organic frameworks.

Programmed ribosomal frameshifting (PRF) is an alternative translation strategy that causes controlled slippage of the ribosome along the mRNA, changing the sequence of the synthesized protein. Here the authors provide a thermodynamic framework that explains how mRNA sequence determines the efficiency of frameshifting.

The Zika viral protease NS2B-NS3 is a crucial target for antiviral drug development due to its role in processing viral polyproteins. Here, the authors utilize crystallographic fragment screening and deep mutational scanning to identify binding sites for resistance-resilient inhibitors.

A ternary catalytic method combining organic photoredox, hydrogen atom transfer and nickel catalysis is reported. This combination can directly arylate the allylic C(sp³)–H bonds of a broad range of readily available olefins. Mechanistic experiments, coupled with density functional theory calculations aid the elucidation of the ternary catalytic cycle and the origin of regioselectivity.

The majority of methods to prepare β-amino acid derivatives require metal-mediated multistep manipulations of pre-functionalized substrates. Now, a metal-free, energy-transfer enabled, highly regioselective aminocarboxylation reaction has been developed, for the single-step installation of both amine and ester functionalities into alkenes or (hetero)arenes. An oxime oxalate ester is used as a bifunctional reagent, supplying C-centred ester and N-centred iminyl radicals.

The potential power of the saturated carbocycle bicyclo[3.1.1]heptane as a beneficial motif for improving the pharmacokinetic and physicochemical properties of drug candidates is demonstrated.