News & Views in 2019

Tertiary amines are poor directing groups for C(sp³)–H activation using Pdⁱⁱ catalysts due to favourable β-hydride elimination pathways. Now, an N-acetyl amino acid ligand is shown to shut down this deleterious pathway, enabling facile arylation of a highly medicinally relevant group of compounds.

The tumour microenvironment has a specific enzymatic fingerprint, which provides opportunities for cancer therapy. Now, two studies show how this unique chemical environment can be used to produce reporter molecules or nanoclusters within the tumour that can subsequently be identified in urine or breath, enabling cancer detection and monitoring.

Synthetic genetic circuits leverage the information processing capability of biological machinery to tackle complex sensing tasks, yet they lack many of the advantages inherent to electrical computation. Now, an interface has been designed that provides an electrical output for synthetic genetic circuits.

Flavin-dependent halogenases catalyse the regioselective formation of carbon–chlorine and carbon–bromine bonds using oxygen and inorganic halide salts. Now, genome mining has led to the discovery of a previously unknown viral halogenase that catalyses the iodination of arenes, thereby providing a rare biocatalytic tool for the formation of carbon–iodine bonds.

Biological receptors distinguish between S- and R-enantiomers and these subtle differences in chirality can lead to vastly different protein affinities. Now, a proteomics approach has been developed that capitalizes on chirality to map enantiomeric probe pairs and provides a rapid and global view of protein ligandability within the cell.

The Catellani reaction is a multi-component cascade sequence, catalysed by palladium and norbornene, which typically uses aromatic starting materials. Now, through the use of a modified norbornene co-catalyst, the scope of this reaction has been extended to alkenyl reagents, enabling the preparation of all-carbon tetrasubstituted olefins.

Hydrogen-bonded organic frameworks can readily encapsulate native enzymes and keep them active beyond biological conditions.

Although transporting a starship crewmember onto the surface of an alien planet is clearly science fiction, quantum state teleportation is not, and has been observed in various systems over the last few decades. Now, electron-spin teleportation has been observed in a carefully designed molecular system, paving the way for such behaviour to be tailored through molecular engineering.

The in situ, nanoscale positioning of a single molecule below the diffraction limit remains a challenge for chemists. Now, two approaches show how this can be accomplished through a combination of super-resolution microscopy and photo-inducible crosslinking chemistry.

Nucleophiles directly substitute alcohols in the Mitsunobu reaction, but the process uses hazardous materials and generates an excessive amount of toxic waste. More than 50 years on from its initial discovery, chemists report a new catalytic version of the reaction, with water as the only by-product.

Frank–Kasper phases are topologically close-packed structures typically found in ordered mixtures of ‘hard particles’ such as metallic alloys. Now, a shape amphiphile has been shown to self-assemble into a Frank–Kasper Z phase, which had so far remained elusive in soft materials.

The biosynthetic pathway that produces the structurally uncharacterized gut bacterial genotoxin colibactin can produce unstable, macrocyclic products; however, the extent to which these structures contribute to colibactin’s biological activities is not yet fully understood. Now, two recent studies have provided new insights and reached distinct conclusions regarding their potential mechanisms of action and relevance for genotoxicity.

Interlocked molecules can exhibit chiral stereogenic elements that are not found in covalently bound systems. Now, the shuttling of the ring in a [2]rotaxane has been shown to result in enantiomeric co-conformations that selectively bind chiral guests.

Interphases that form on the anode surface of lithium-ion batteries are critical for performance and lifetime, but are poorly understood. Now, a decade-old misconception regarding a main component of the interphase has been revealed, which could potentially lead to improved devices.

Proteins are biosynthesized from α-amino acids using hefty biological machinery, but the origin of this process on the early Earth is unclear. Now, a bottom-up approach for forming peptides, taking place under mild, prebiotically-plausible conditions, has been developed. This strategy uses α-aminonitrile precursors, bypassing α-amino acids entirely.

Due to the high oxidation potential of gold, the development of dual gold/photoredox-catalysed processes has been limited by the need for an easily reduced radical source. Now, discovery of an energy transfer photoexcitation process overcomes this limitation, enabling the oxidative addition of iodoalkynes onto organogold intermediates.

Precipitation processes enable the fast preparation of a variety of inorganic materials, although typically with little control over their morphology. Now, their one-, two- or three-dimensional growth has been promoted simply by tuning the electrolytic dissociation of the reactants and the supersaturation of the solution.

Aqueous batteries hold promise for large-scale energy storage, but are often maligned because of their low energy densities. Now, a demonstration of halogen conversion–intercalation chemistry inside graphite has blazed a trail for high-energy aqueous batteries.

The chemical functionality necessary for the origin of life may have emerged from simple reactions assembled into complex networks. Now, it has been shown that prebiotically relevant heterogeneous reaction networks can generate robust oscillations within complex mixtures comprised of precursors that do not oscillate on their own.