Articles

Selective oxidation of biomass-derived precursors has been reported but requires elevated temperatures and pressures of O₂ and strongly alkaline conditions. This study develops an antenna–reactor plasmonic photocatalyst (RuPt on TiN) for the selective conversion of HMF to FDCA using near-infrared irradiation in the absence of base.

Photoexcited nitroarenes are traditionally consumed as reactive intermediates in transformations. Now, it is shown that simple and cheap nitroarenes can be used as energy transfer photocatalysts in reactions such as E-to-Z alkene isomerization and [2 + 2] intramolecular cycloadditions.

Electrocatalytic CO₂ reduction is typically studied at laboratory scale under ambient conditions; however, temperature and pressure may have a profound impact on the mechanism of this reaction and on its relevance to industrial applications. This study uses a custom temperature- and pressure-adjustable cell to reveal a chain growth mechanism emerging on copper electrodes at elevated temperatures and pressures.

Catalytic asymmetric all-carbon-based inverse-electron-demand Diels–Alder reactions are challenging. Now, transition metal catalysts enable formal inverse-electron-demand [4+2] cycloaddition reactions of Morita–Baylis–Hillman carbonates with 1,3-unsaturated compounds to afford chiral cyclohexene derivatives.

Cross-dehydrogenative coupling (CDC) allows the efficient construction of C−C and C−heteroatom bonds. Now, single-platinum-atom-decorated graphitic carbon nitride is applied as a heterogeneous photocatalyst for CDC reactions between (hetero)arenes and nucleophiles without external oxidants.

Directed hydrogen exchange is one of the main strategies for accessing isotopically labelled organic scaffolds, but the rationale for deuterium source selection has not been fully explored yet. Now the authors reveal the influence of the deuterium source in base-assisted site-selective C–H deuteration reactions across substrates in cobalt catalysis.

There is growing interest in the direct conversion of carboxylic acids into nitriles. Now the authors report a mild Mg- and Pd-cocatalysed method compatible with multiple functional groups, using urea as the nitrogen source.

The notion that catalysts are static entities that barely change under operation is still prevalent although it is often not true. Here, a range of operando and in situ techniques reveals the dynamic nature of Co₃O₄ during the oxidation of 2-propanol to acetone, unveiling a network of interconnected solid-state processes, such as exsolution, diffusion or void formation, that govern the catalytic performance.

The T4 td-PIE system is a promising platform for circular RNA synthesis, but the dynamic mechanism of the T4 td group I intron during circularization remains unclear. Now, cryo-EM structures of both the linear and circular forms of the T4 td intron are solved, revealing key conformational shifts essential for RNA circularization.

Thermodynamically disfavoured substituted cyclohexane compounds often display superior physical and bioactive properties to their isomeric counterparts. Now their synthesis is achieved by Ni-catalysed coupling of substituted methylenecyclohexanes with electrophiles under kinetic control.

Radical repositioning to activate remote bonds is underdeveloped in synthetic biocatalysis. Now a photobiocatalytic system couples light-driven single-electron transfer and the relocation of unpaired electrons to activate remote C–C and C–H bonds for enzymatically controlled enantioselective acylation.

The creation of artificial metalloenzymes compatible with complex biological settings could enable broad applications. Now a de novo-designed artificial metalloenzyme containing an abiological ruthenium cofactor is reported and optimized for ring-closing metathesis in the cytoplasm of whole cells.

The application of DNA phosphates to mediate asymmetric reactions is underdeveloped in synthetic chemistry. Now, DNA phosphates are designed to catalyse enantioselective fluorination, Mannich and photo-induced cross-dehydrogenative coupling reactions in water driven by ion-pairing interactions.

The Heck reaction is widely used in modern organic chemistry. Here the authors provide an alternative approach to common transition-metal catalysis, leveraging access to Bi(II) species thanks to bismuth’s photophysical properties.

Constructing C(sp³)–C(sp³) bonds using non-prefunctionalized substrates as radical precursors is challenging. Now an ene-reductase and an organophotoredox catalyst work together to enable the enantiodivergent hydroalkylation of electron-deficient C(sp³)–H bonds via radical intermediates generated from carbanions.

Probing transient intermediates and deriving subsequent mechanistic and kinetic analyses is very challenging. Now, Pd–H* intermediates on palladium nanocubes are identified at the single-particle level by means of single-molecule reaction imaging, evidencing intra- and interparticle heterogeneity and hydrogen spillover events.

The Mannich reaction has long been used by chemists for the synthesis of stereoselective synthesis of β-amino-carbonyl compounds. Here, the authors show a catalytic homo-Mannich reaction of cyclopropanols with in situ-formed imines, furnishing chiral 2,6-disubstituted piperidines in good yields with high diastereoselectivities due to the use of a diketiminate-complexed copper.

Darwinian evolution has shaped life on our planet through natural selection. Here, the authors report on the combination of self-replication, mutation and protometabolism in an out-of-equilibrium abiotic chemical system that can lead to natural selection for protometabolic activity.

Deuterated bioactive compounds are important as diagnostic tools and pharmaceuticals, but current methods of development are limited. Here the authors report how a silicon Lewis acid and a tertiary amine base act as a frustrated Lewis pair to catalyse the hydrogen exchange reaction for the deuteration of amides and esters.

Artificial photobiocatalytic reactions are appealing but sometimes suffer from non-enzymatic side reactions. Now a photoenzyme for enantioselective [2 + 2] photocycloaddition of 2-naphthyl derivatives is reported and combined with designed quenchers that shut down the competing enzyme-free racemic reaction.