Articles

Delocalized radical systems are appealing for controlling stereoselectivity in organic synthesis. Here the authors report on a Co(II)-based enantioselective radical system for the dearomative 1,7-conjugate amination of readily available 4-vinylphenols with aryl azides.

Tandem electro-biocatalytic systems present a versatile platform for producing a variety of synthetic products using CO₂ as a starting material. Here direct ocean carbon capture is incorporated into an electrolysis scheme to produce formic acid from CO₂ dissolved in seawater that is subsequently converted to succinate in a bioreactor.

The activity and stability of supported metal catalysts is in large part influenced by their interaction with the support. Now, neural network molecular dynamics simulations are combined with interpretable machine learning to reveal the governing factors of metal–support interactions for Pt nanoparticles on various oxide supports, identifying key features and proposing sinter-resistant supports.

Hexopyranose cleavage is a crucial step in carbon metabolism. Here the authors report the discovery and characterization of metalloenzyme Art22, which is involved in the sugar moiety modification of aurantinin B, an antibacterial agent from Bacillus.

It is challenging to design machine learning potentials for heterogeneous catalysis that are universal, reactive and have high accuracy. Now, an element-based machine learning potential relying on a random exploration via an imaginary chemicals optimization sampling strategy is put forward, and is successfully demonstrated for a range of applications.

Molecular organometallic catalysts typically struggle to activate only one of two identical C–H bonds in arenes for mono-selective C–H activation. Now mono-selectivity has been achieved for Pd(II)-catalysed ortho- or meta-C–H activations using commercial proteins or designed peptides as ligands.

Strategies for asymmetric control in electrosynthesis involving radicals are sought after. Now asymmetric Lewis base catalysis is combined with electrochemistry, enabling the oxidative radical cross-coupling of esters with silyl enol ethers and affording γ-keto esters in high enantiomeric excess.

Optimizing devices for electrochemical CO₂ reduction requires a comprehensive and quantitative understanding of the microenvironments where the reactions occur. Now, a multiscale modelling approach that explicitly accounts for electrolyte effects at all scales is developed and showcased for the electroreduction of CO₂ on silver.

Azetidines are four-membered saturated N-heterocycles that are of interest in drug discovery and medicinal chemistry. Here the authors report how sulfamoyl fluoride substituents tune the reactivity of acyclic imine-derived triplet intermediates for the synthesis of azetidines via a [2 + 2] photocycloaddition reaction with alkenes.

Directing group strategies for selective dearomatization of unactivated aromatic π-systems have remained elusive. Now a homogeneous ruthenium catalyst, aided by a removable directing group, enables the site-selective hydrogenation of less reactive arene moieties in polyaryl compounds.

Electrocatalytic CO₂ conversion offers opportunities for producing sustainable fuels and chemicals, but achieving strong performance with realistic CO₂ sources remains a challenge. Here a system is designed to use high-pressure captured CO₂, and achieves 85% Faradaic efficiency and high-purity C₂H₄ for over 1,500 h.

The O-alkylation of tertiary alcohols with racemic tertiary electrophiles to access chiral hindered dialkyl ethers has remained elusive. Now this synthetic challenge has been accomplished by copper-catalysed C–O cross-coupling between tertiary haloamides and alcohols using designed ligands.

Anodic pulsing during electrocatalytic CO₂ reduction has been shown to enhance activity and selectivity towards hydrocarbons and alcohols on copper yet the nature of the active sites remains unclear. Here, correlated spectro-microscopy in a quasi in situ experimental set-up provides information on the formation of specific facets and oxidation states under reactive conditions.

Understanding the interplay between the catalyst surface and its microenvironment is important for the development of electrocatalysis. Here, in situ Raman spectroscopy is used to resolve the interactions between copper, surface-adsorbed hydroxyl, electrolyte cations and interfacial water during electrocatalytic CO reduction.

Current industrial methods of ethylene glycol production generate substantial CO₂ emissions. Here electrocatalytic ethylene-to-ethylene glycol conversion is coupled to electrochemical CO₂ capture, decreasing carbon intensity by an order of magnitude.

Alternative fuels such as biomethane are attractive, although their combustion generates pollutants such as formaldehyde that impair conventional abatement technologies. This study elucidates the impact of HCHO during the selective catalytic reduction of NO_x over Cu-SSZ-13 catalysts, revealing important structural and mechanistic aspects.

Expanding the methods for constructing artificial enzymes is of high interest. Now a photoactive cofactor is designed that mimics NAD⁺, allowing its insertion into a range of NAD⁺-binding protein scaffolds to catalyse inter- and intramolecular [2 + 2] cycloaddition reactions.

The mechanism by which the [NiFe₄S₄] cluster of carbon monoxide dehydrogenases (CODHs) catalyses CO₂ reduction is poorly understood. Now the structures of all catalytically relevant states of a CODH are solved, revealing the dynamics of the cluster during turnover and the role of Ni in CO₂ activation.

Despite the ease of fine-tuning their reactivity, high-performance homogeneous photocatalysts competent for acetylene semihydrogenation are scarce. Here the authors introduce an effective cobalt catalyst for the production of polymer-grade ethylene, which is amenable to scale-up in a continuous-flow photoreactor.

Aqueous electroconversion of biomass derivatives to polymer precursors has been demonstrated at the laboratory scale with low yield. Here a solid polymer electrolyte reactor is engineered to limit side reactions, yielding a high rate and and a high product concentration in a 4.3-kW pilot-scale platform.