Research articles

The synthesis of allenes through 1,4-difunctionalization of 1,3-enynes typically requires preformed organometallic species, high temperature or specific alkyl radical precursors. Now an electrochemical multicomponent protocol for the chemo- and regioselective 1,4-difunctionalization of 1,3-enynes is reported, which uses alkyl bromides with aryl bromides, alkyl bromides or H₂O/D₂O as reagents for 1,4-difunctionalization.

Piperidine heterocycles are widely prevalent in drug molecules; however, their synthesis remains challenging. Now, a general approach for N-(hetero)aryl piperidine synthesis using isolable iminium salts is reported. A variety of substituents are installed at the C2 and C3 positions, giving access to densely functionalized piperidines that are challenging to obtain using other methods.

Atomically precise graphene fragments are synthesized by using a radical-mediated coupling approach. One open-shell doublet graphene fragment forms a persistent bilayer assembly with highly delocalized 32-centre-2-electron pancake bonding.

Visible-light-driven dual photoredox catalysis often uses expensive metals, such as iridium. Now, a photocatalytic approach using a Ni single-atom carbon nitride catalyst is reported for the C–O cross-coupling of carboxylic acids and alkyl halides, demonstrating broad functional group tolerance, short reaction times, facile recovery and excellent stability.

The synthesis of phosphorous compounds in the 5+ oxidation state typically relies on energy-consuming processes using white phosphorus (P₄). Now, a simple approach that cleaves P–O bonds in ubiquitous P^V sources to form a PO₂⁺ phosphorylation agent enables the redox-neutral synthesis of various P^V chemicals.

Nature uses complex supramolecular reaction networks to regulate structure formation. Now, by creating a photolytic reaction cascade with competing redox pathways, different hierarchical assemblies can be tailored based on a single molecular identity.

By combining coordination, cluster and colloidal chemistry, precision synthesis is realized in cation-exchange reactions of nanoclusters (Cu₂Se to CdSe). The precise transformation unveils the origin of chirality and polarity in semiconductor nanomaterials and enables atomic visualization of complex reaction mechanisms.

Cross-coupling reactions are among the most widely used synthetic methods in medicinal chemistry; however, they typically form bonds with C(sp²)-hybridized atoms. The resulting molecules often have suboptimal physicochemical and topological properties. Here virtual and experimental libraries of products from benzylic C(sp³)–H cross-coupling are shown to access underpopulated 3D chemical space.

Carbon-negative biomanufacturing is typically hampered by narrow product scope and light-induced decomposition. Now, an integrated photosynthetic carbon sequestration and cellular catalysis strategy for CO₂ valorization are reported. Multiple gene editing and a high-throughput workflow have facilitated its application to the biocatalytic production of styrene, intracellular unstable aldehydes and photosensitive molecules from CO₂.

trans-Bis-silylation of alkynes is underdeveloped compared with cis-bis-silylation. Now, a Pd-catalysed method for the trans-bis-silylation of terminal alkynes is reported using disilane reagent 8-(2-substituted 1,1,2,2-tetramethyldisilanyl)quinoline to selectively form trans-bis-silylated alkenes. Mechanistic studies reveal that the reaction probably proceeds through a combined cis-bis-silylation and Z/E isomerization process.

The synthesis of topological molecular carbons with persistent chirality is challenging. Here, a triply twisted Möbius carbon nanobelt was synthesized and its two enantiomers were isolated, showing a large absorption dissymmetry factor.

Twisted aromatic belts provide unique topologies and complex chiralities for nanocarbon materials. Now, rhodium-catalysed asymmetric [2 + 2 + 2] cycloadditions enable the stereoselective synthesis of doubly, triply and quadruply twisted aromatic belts.

Polyoxoniobate (PONb) clusters are ideal candidates for synthesizing 2D clusterphenes but niobate reactivity is low. Now, 2D hexagonal PONb-clusterphenes have been prepared through a wet-chemical synthesis at ambient conditions, providing atomically precise models for examination of cluster electronic structures.

The synthesis of ionogel membranes is challenging to control. Now, a general strategy is developed for the layer-by-layer exfoliation of 2D ionogel membranes through controlled solvent-induced supramolecular self-assembly. This strategy enables the rapid and scalable fabrication of ionogels with designable shapes, controllable thicknesses, high ionic conductivity and promising applications.

The fabrication of organic polymers in single-crystal form is challenging. Here a rare single-crystal porous polymer with solution processability is synthesized by combining a one-dimensional chain structure, dynamic covalent bonds and various intermolecular interactions. This polymer is used as a coating on fabric for ammonia capture.

The backbone stereoregularity that dictates a broad range of polymer properties cannot be readily controlled in radical polymerizations. Now, bimetallic catalysts containing covalently bridged rare earth and cobalt complexes enable stereocontrolled living radical polymerization of acrylamides tethered with diverse polar and ionic pendant groups.

Elongation of acenes with linearly fused benzene rings is a synthetic challenge. Now, the use of a metal–organic framework enables the synthesis of polymeric precursors, which undergo thermal transformation to form polyacenes.

Graphene-like molecules with a zigzag periphery are synthetically challenging. Now, a programmable zigzag π-extension strategy to rapidly assemble graphene-like molecules is reported based on rhodium-catalysed sequential C2–H and C8–H activation-annulation of naphthalene ketones, using acetylenedicarboxylates as the C2 insertion unit.

Synthesizing superstructures with precisely controlled nanoscale building blocks is challenging. Here the assembly of superstructures is reported from atomically precise Ce₂₄O₂₈(OH)₈ and other rare-earth metal-oxide nanoclusters and their multicomponent combinations. A high-temperature ligand-switching mechanism controls the self-assembly.

Controllable synthesis of 1D metal halide perovskite nanocrystals is challenging due to their structural symmetry and ionic crystal nature. Now, a general platform of cylindrical unimolecular nanoreactors has been developed to craft a variety of 1D perovskite nanorods with tailored dimensions and compositions.