Research articles

A versatile solar-driven hybrid photoelectrochemical platform has been developed for the simultaneous conversion of greenhouse gas CO₂ and waste plastics into value-added fuels and chemicals with high efficiency and selectivity.

The targeted synthesis of heterostructured nanomaterials is required to meet the need of various applications, and the rational design of such nanomaterials is crucial. Now, cation exchange reactions have been designed to maximize product diversity for combinatorial heterostructure discovery. Synthetic guidelines are outlined, translating microscopic observations into high-yield samples.

Direct ribosylation of nucleobases for regioselective ribonucleoside synthesis is a challenge. Now, a prebiotic Ti-catalysed ribosylation of nucleobases is reported, providing selective access to N9 purine nucleosides. Mechanistic analysis reveals key substrate–surface interactions are the origin of the regiocontrol.

The use of acyl functional groups as nucleophilic synthons in transition metal-catalysed carbometallation of unsaturated hydrocarbons remains challenging. Here, nickel-catalysed acylzincation reactions of alkynes and alkenes with organozinc reagents under 1 atm of CO are developed, featuring high functional group tolerance, a broad substrate scope and mild conditions.

A combined copper- and palladium-catalysed atropselective arylboration of alkynes is reported. This method uses B₂pin₂ and sterically hindered aryl bromides for the stereoselective and regioselective synthesis of axially chiral tetrasubstituted alkenylboronates. Mechanistic studies reveal that the stereocontrol originates from a higher-order palladium intermediate.

Preventing metal deposition by cathodic reduction under direct current electrolysis conditions is a formidable challenge in transition-metal-catalysed electrosynthesis. Now, an asymmetric-waveform alternating current (a.c.) electrolysis approach is developed for silver-catalysed C–H phosphorylation where this a.c.-based approach regenerates the silver catalyst and keeps the catalyst loading balanced during the reaction.

Single-atom catalysts (SACs) are attractive for a variety of applications but their synthesis remains challenging. Now, a scalable and economical 3D-printing approach has been developed for producing libraries of SACs using a variety of metals, coordination environments and spatial geometries.

Stereodefined 1,2-dimetallated alkenes are underexplored in organic synthesis due to their relatively low stability. Now, the reductive anti-1,2-dimetallation of alkynes provides access to trans-1,2-dimagnesio- and 1,2-dialuminoalkenes. The process uses sodium dispersion as a reducing agent with organomagnesium and organoaluminium halides as reduction-resistant electrophiles.

Reactions induced by σ-aromaticity are uncommon compared with those induced by π-aromaticity. Now, a π- and σ-aromaticity relay strategy is developed to realize the ring contraction of metallacyclobutadiene to metallacyclopropene. This reaction involves the release of π-antiaromaticity to afford a π-aromatic intermediate, followed by ring reclosure to form σ-aromatic metallacyclopropene.

Controlling diastereodivergent light-driven processes remains synthetically challenging. Here, we disclose how the light source and steric parameters can be used to control the diastereoselectivity of [2 + 2] heterocycloaddition processes, such as in Paternò–Büchi reactions, and provide access to previously inaccessible stereochemical variants.

Mechanical cleavage of layered materials to obtain two-dimensional (2D) sheets is restricted to materials with interlayer interactions dominated by van der Waals (vdW) forces. Here, calendering is used to weaken interlayer binding in non-vdW layered structures (metals, semiconductors and superconductors) allowing mechanical exfoliation to obtain 2D sheets with thickness-dependent properties.

Enantioselective difunctionalization of alkenes mediated with radicals and using selective C–H bond activation remains unexplored. Now, an asymmetric 1,2-oxidative alkylation of conjugated dienes, based on direct functionalization of strong and neutral C(sp³)–H bonds, is reported using a combination of hydrogen atom transfer and copper-catalysed reactions.

Automated organic synthesis is often limited to making simple molecules, requiring a small number of synthetic steps, because of the complexity and variety of organic molecules. Now, a robotic platform has been instructed to build complex structures, such as the core fragment of (+)-kalkitoxin, in a stereochemically controlled and iterative manner.

Asymmetric C–H functionalisation provides efficient synthetic routes to chiral metallocenes; however, these methods are often limited by the substitution patterns that can be accessed. Now, a Rh-catalysed enantioselective C–H arylation provides access to chiral 1,2-disubstituted and 1,3-disubstituted metallocenes via kinetic resolution of pre-functionalised metallocenes.

Stereoselective alkynylallylic substitution reactions are underexplored compared with propargylic and allylic substitutions. Now, a copper-catalysed intermolecular and decarboxylative alkynylallylic amination, alkoxylation and alkylation strategy has been developed for the synthesis of chiral 1,4-enynes. Mechanistic studies suggest that the formation of a dinuclear copper allenylidene is the rate-limiting step.

Torus knots are assembled in a contra-helical tubular manner by coaxially nesting a small multistranded helix within a larger reverse helix. This approach enables the near-quantitative one-step syntheses of four iron(II)-templated trefoil knots. The spin-crossover properties of the iron(II) centres in the knots are tuneable by altering the intramolecular strain.

Alternaric acid is a known starting point for herbicide development. Now, the development of a total synthesis enables structure–activity relationship profiling of compound libraries, which, combined with phenotypic screening and molecular modelling, identifies lead compounds with enhanced herbicidal activity compared with alternaric acid.

Developing highly elastic and conductive hydrogels is challenging, especially for use in harsh environments including organic solvents and extreme temperatures. Now, a self-assembly and in situ polymerization method is reported for the fabrication of highly compressible and environmentally adaptive conductive hydrogels with concrete-type constituents and high-tortuosity interconnected cellular architectures.

The complexity of carbohydrate structures makes their synthesis challenging. Now, an automated glycan synthesizer is reported which is capable of preparing a library of bioactive oligosaccharides, including a fully protected fondaparinux pentasaccharide. Furthermore, the synthesizer can rapidly assemble arabinans up to 1,080-mer size, starting from monosaccharide building blocks.

Two-dimensional materials have many desirable properties but controllable synthesis is difficult. Now, a flux-assisted growth approach has been designed to reproducibly prepare high-quality, atomically thin materials. Eighty atomically thin composite flakes have been prepared by this approach.