Research articles

The production of fluorination agents generally involves the formation of toxic hydrogen fluoride. Now, a mechanochemical protocol to decompose the fluoropolymer polyvinylidene fluoride has been developed, generating potassium fluoride as a fluorinating agent. This approach provides a safer and sustainable fluorination strategy for efficient S–F, C(sp²)–F and C(sp³)–F bond formation.

Polyunsaturated fatty acids (PUFAs) are attracting considerable interest because of their diverse structures and properties. Now a method to access a wide array of PUFAs by full solid-phase synthesis has been developed and used to discover an anti-inflammatory fatty acid.

In drug development, altering the ring sizes and editing the stereochemistry of chiral heterocycle scaffolds in lead compounds are effective but challenging. Now an adaptive dynamic kinetic resolution strategy has been developed that enables the integration of multi-contiguous stereocentres and the assembly of complex polycycles such as martinellic acid.

Biocompatible chemistry merges chemo-catalytic reactions with cellular metabolism for sustainable small-molecule synthesis. Now a biocompatible Lossen rearrangement has been demonstrated to control bacterial cell growth and chemistry and applied to the remediation and upcycling of polyethylene terephthalate plastic waste in whole-cell reactions and fermentations to produce valuable industrial chemicals, including the drug paracetamol.

Despite recent advances in primary sulfonamide synthesis, approaches using primary amines as starting points for direct sulfonamide construction remain elusive. Now a formal SO₂ insertion into the C–N bond of primary amines has been developed, using an anomeric amide reagent for both C–N cleavage and S–N bond formation.

The synthesis and isolation of compounds featuring lanthanide–carbon triple bonds remain challenging. Now a cluster featuring a cerium–carbon triple bond has been stabilized inside a C₈₀ fullerene cage. The solid-state structure of the compound reveals a cerium–carbon bond distance of 1.969(7) Å.

Despite advances in polymer science, reversible formation and control of linear conjugation in polymer backbones remain elusive. Now, copolymerizing lactone-functionalized xanthene units with π-conjugated building blocks has been shown to produce polymers capable of reversible, stimuli-responsive conjugation switching, enabling tunable semiconducting behaviour and offering a promising strategy for designing smart, responsive polymeric materials.

C–H functionalization is a key reaction in organic synthesis. Now a selenoxide reagent has been developed for the formation of arylselenonium salts via C–H functionalization of DNA conjugates with high selectivity. The arylselenonium salts participate in various transformations to forge new C–C and C–X bonds.

Target-oriented syntheses of natural products usually require the design of individualized routes that are tailor-made for the specific targets. Now, a strategy that runs counter to this conventional wisdom has been achieved. Exploiting a biocatalytically installed alcohol, several abiotic skeletal rearrangements have been designed to prepare three structurally disparate terpenoid natural products.

C=O cleavage of formamides and full transfer of the resulting fragments into final products are highly appealing, particularly in multi-component reactions for the synthesis of structurally complex molecules. Now three-component reactions of diazo compounds with allylic substrates and formamides are presented, giving extensively reorganized products via multi-step relay.

The functionalization of carbon–carbon bonds in amines remains an important challenge in organic synthesis. Now a borane-catalysed method has been developed that enables the insertion of alkynes into the alkyl C–C bonds of amines, providing a versatile approach for the ring expansion of cyclic amines and chain elongation of acyclic amines.

The extracellular matrix (ECM) is assembled through liquid–liquid phase separation and directed phase transition. Now—inspired by tropoelastin—a designer minimalistic model incorporating alternating hydrophobic moieties and crosslinking domains can template the assembly of a biomimetic matrix that mimics the ECM, promoting the mechanosensing of stem cells.

Information-bearing templates that catalyse the assembly of complex macromolecules are a central motif of natural biochemistry, but their power remains largely unexplored in synthetic contexts. Enzyme-free templating of DNA dimerization has now been demonstrated, using DNA nanotechnology to ensure that the templates are effective information-propagating catalysts.

Proteins with small structural modifications at specific sites are valuable, yet challenging to access by chemical methods. Now, tyrosine-selective single-atom modifications on proteins have been achieved by C–H functionalization using a rationally designed selenoxide to introduce a versatile selenonium linchpin for further transformations.

Ultramicroporous solids hold great promise for hydrocarbon separation, but uncovering their design principles remains challenging. Now, a series of ultramicroporous zirconium metal–organic frameworks with tunable microporosity and pore structure have been prepared by combining isophthalate-based octatopic or hexatopic organic linkers and Zr₆ nodes; these materials can separate hexane isomers as a function of branching.

Building protocells with intricate cellular organization and cell–cell interactions is a crucial step in attempts to replicate cytomimetic functions. Now it has been shown that interfacial assembly of porous metal–organic frameworks on protocell coacervates facilitates complex biomolecular organization, regulated protocell communications and structured protocell assembly.

Gold redox catalysis is an attractive synthetic method but challenging due to the high redox potential of Au(I)/Au(III). Now, a bidentate N-ligand-assisted gold redox catalysis using H₂O₂ as oxidant has been developed. It can be applied to various coupling reactions, including C(sp)–C(sp) cross-coupling, alkynylative cyclization and bicyclization coupling.

Models of abiotic RNA replication suffer from inherent product inhibition arising from the high stability of RNA duplexes. Now, it has been shown that RNA trinucleotide substrates undergoing simple physicochemical cycles can overcome this problem, enabling open-ended replication of defined and random RNA sequences by a polymerase ribozyme.

Polydienes are essential in industry but rely on a complex synthesis involving catalysts and solvents. Now it is shown that photo-melt-bulk polymerization enables the solvent- and catalyst-free synthesis of controlled high-molecular-weight polydienes by combining chain growth and the coupling of stable biradicals, advancing sustainable materials development.

Fluorogenic RNA aptamers such as Mango are powerful tools for RNA imaging. An ultrabright RNA-activated fluorophore with improved photophysical performance has now been developed using a structure-informed, fragment-based screening approach. This system was studied using high-resolution crystallography and applied to image RNA in cells.