Research articles

Degradable polymers are needed to overcome the environmental persistence of the materials. Now, cyclic–acyclic monomers metathesis polymerization is reported to produce degradable thermoset, thermoplastic and elastomeric polymers. The material properties and degradability of the polymers are investigated after different treatment methods during their synthesis.

Selective oxidation of ring C–H bonds is an attractive route to functionalized cyclic amines, which are versatile intermediates in drug synthesis. Now, engineered P450 enzymes, designed with computational guidance to disfavour undesired products, are reported to oxidize all unactivated C–H bonds in cyclic amines with high selectivity.

Developing a bench-stable glycosyl donor of multifunctional sugar residues that can be activated under mild conditions is a challenge in carbohydrate chemistry. Now, stable glycosyl sulfones are used in a photoinduced method for desulfonylative cross-coupling to prepare a range of C- and S-glycosides.

Developing enantiodivergent catalysts capable of preparing both enantiomeric products from one substrate in a controlled fashion is challenging. Now, a manganese(III)-salen complex with a chiral photoswitchable phosphate counterion is reported for the epoxidation of alkenes in a stereoselective manner, where irradiation with light allows access to either enantiomer of the epoxide.

Plastic waste poses a serious economic, ecological and environmental threat. Here, non-recyclable, post-consumer microplastics are used as an electron feedstock for biosynthetic reactions in a photoelectrocatalytic system. The microplastics are simultaneously broken down into organic fuels, meaning that this system provides valuable chemicals at both the anodic and cathodic sites.

β-hydride and β-heteroatom eliminations are elementary steps in many catalytic reactions used in the synthesis of drug molecules and polymers. However, the elimination processes often compete leading to unpredictable outcomes. Here, a series of mechanistically informed selection rules are developed to selectively achieve the desired elimination.

α,α-Dideutero carboxylic acids are common precursors for isotopically labelled molecules; however, their synthesis often requires high temperatures with strong bases or precious metals. Now, the α-deuteration of carboxylic acids has been developed under mild conditions using a ternary catalyst system of K₂CO₃, pivalic anhydride and 4-dimethylaminopyridine.

Current synthesis of 2D crystalline superconductors mainly limits them to layered materials. Now, crystalline, non-layered 2D PdTe has been synthesized by inducing interfacial reactions at a solid–solid interface, exhibiting 2D superconductivity with a thickness-dependent onset critical temperature of ~2.56 K.

Synthesis of seven-membered carbocycles via (4 + 3)-cycloaddition reactions is often challenging due to the instability of the zwitterionic three-carbon component required. Now, a copper-catalysed enantioselective (4 + 3)-cycloaddition of 2-amino cations with dienol silyl ethers is reported, providing seven-membered carbocycles in good yields and with excellent enantiocontrol.

Anion-binding interactions are prevalent in nature but not commonly used in polymerizations. Now, an anion-binding catalytic strategy for living cationic polymerization is reported. Selenocyclodiphosph(V)azanes act as hydrogen-bond donors to reversibly activate dormant covalent bonds, and enable control of the equilibrium between the dormant and active species, which ensures precision polymer synthesis.

Controlling the enchainment of ether and carbonate segments during copolymerization of CO₂ and epoxides is rarely possible. Now, precise control of enchainment is realized by tuning the structure of an organoboron catalyst and the reaction conditions. Mechanistic and computational studies probe the origin of the unique ABB microstructure of the polymer.

Dual-atom catalysts are promising for CO₂ reduction reactions; however, sluggish kinetics limit practical applications. Now, a Ni dual-atom catalyst has been synthesized, realizing efficient electrocatalytic CO₂ reduction with a CO partial current density of ~1 A cm² at >99% Faradaic efficiency.

[10]annulene derivatives are typically non-planar and non-aromatic, with aromatic planar variants suffering from kinetic instability. Now, the synthesis of a planar and aromatic dehydro[10]annulene featuring a fused cyclopropane and an internal alkyne is reported. The resulting hydrocarbon is bench stable and can be stored for extended periods of time.

The integration of two-dimensional semiconductors and arbitrary materials or architectures offers the possibility to enhance the functionality of a material and improve device performance. Now, a general synthesis route is reported for heteroepitaxial growth of semiconducting 2H-MoTe₂ films on arbitrary single-crystal substrates and three-dimensional architectures without the limitation of lattice matching and a planar surface.

Preparing two-dimensional heterolayers by vertically stacking chemically different layers with multiple anions remains challenging. Now, a general approach for the synthesis of heterolayered oxychalcogenides using molten hydroxides as unconventional solutions for the rapid stacking of oxide and chalcogenide layers with precise composition control is demonstrated.

Quantum chemical calculations are typically used in synthetic organic chemistry to probe reaction mechanisms and propose stereochemical models. Now, a strategy to develop chemical reactions using quantum chemical calculations is reported. This study demonstrates in silico reaction screening with difluorocarbene, leading to a method for the synthesis of fluorinated N-heterocycles.

The performance of single atom catalysts (SACs) is controlled by the metal single atom sites, but the role of the matrix material is less understood. Now, a hard-template synthesis is reported, enabling control of the atomic and mesoporous structures of SACs and the probing of matrix materials with either 2D or 3D diffusion channels.

Functionalization of C–H bonds through direct hydrogen atom transfer (HAT) photocatalysis is an attractive synthetic reaction; however, many methods suffer from low catalytic efficiency. Now, the efficiency of direct HAT photocatalysis using photocatalyst eosin Y combined with Brønsted acids is reported, enabling the functionalization of unactivated C(sp³)–H bonds.

Inspired by molecular catenanes, mechanically interlocked gold nanocatenanes are synthesized starting from triangular gold nanoplates. The interlocked gold nanocatenanes have intriguing optical and mechanical properties, originating from their plasmonic nanomechanical bonds.

The construction of C–C bonds with regio- and stereoselectivity is paramount in natural product synthesis and metal-catalysed asymmetric allylic alkylation reactions have played a key role, with high C3 selectivity demonstrated in butenolide synthesis. Now, a palladium-catalysed C5-selective method is reported, providing direct and highly enantioselective access to a range of diversely substituted butenolides.