Research articles

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.

High-throughput synthesis of polypeptides through ring-opening polymerization of N-carboxyanhydride is challenging. Now a diversification approach is developed based on the post-polymerization modification of a selenium-containing polypeptide. With the assistance of automation and model-guided optimization, this approach enables the discovery of functional polypeptides from chemical space with little previous knowledge.

Ortho-C–H and meta-C–H functionalization of arenes is well developed; however, para-C–H functionalization is more challenging. Now, a method for the synthesis of para-functionalized anilides from arylhydroxylamines and O- and S-nucleophiles is reported. The process uses fluorosulfuryl imidazolium triflates at low temperature and probably comprises O-fluorosulfonation, followed by N–O bond cleavage and nucleophilic addition.

Electrochemical routes to commodity chemicals are increasingly important to decarbonize the chemicals industry. Now, an electrochemical route to sulfonate products using CO₂ and SO₃²⁻ as building blocks has been reported, expanding the scope of electrochemical CO₂ reduction.

Alkyl alcohols are attractive surrogates for alkyl halides in the Suzuki–Miyaura cross-coupling reactions, but methods to activate the C–O bond are underdeveloped. Now a Ni-catalysed arylation is reported that uses aryl boronic esters and tertiary alcohols, through in situ alcohol silylation.

C14-functionalized steroids are pharmaceutically valuable, but their synthesis is challenging. Now a chemoenzymatic route is reported featuring a key biocatalytic C14α-hydroxylation, enabled by protein engineering of a C14α-hydroxylase (CYP14A) from Cochliobolus lunatus. Dehydration and olefin functionalization of the biocatalytic reaction products provides C14-functionalized steroids.

The synthesis of ammonia from dinitrogen is a vital reaction. Now, ligands prepared based on density functional theory calculations are used with a molybdenum trichloride complex for the production of up to 60,000 equiv. ammonia based on the catalyst, with a molybdenum turnover frequency of 800 equiv. min⁻¹.

The tailored synthesis of heterostructured intermetallic nanomaterials (iNMs) is challenging. Now, a galvanic replacement strategy is reported for the construction of a library of iNMs. Layered interfacial growth produces intermetallic heterostructures with controllable compositions, structures and interfaces.