Articles

Palladium-catalysed C(sp³)–H amination reactions of carboxylic acids are challenging due to N-coordination often outcompeting the carboxylic acid directing effect. Now, the development of chlorinated pyridine–pyridone ligands for palladium-catalysed methylene C(sp³)–H lactamization and cycloamination is reported, enabling the synthesis of lactams and cyclic amines.

Quaternary oxides can be synthesized from a variety of precursors, but there is a poor understanding of how to design efficient synthesis recipes. Here a strategy to navigate high-dimensional phase diagrams in search of the best precursors for quaternary oxide materials is reported and validated experimentally by a robotic laboratory.

The making of mirror-image versions of naturally occurring cyclodextrins (CDs) is challenging and constitutes an untouched goal of the CD community. Now a concise approach is developed for the diastereoselective synthesis of three mirror-image CDs in an efficient and scalable manner.

Methods for enzymatic C–F bond formation are rare. Now an enzymatic method for enantioselective C(sp³)–F bond formation is reported, through reprogramming non-haem iron enzyme (S)-2-hydroxypropylphosphonate epoxidase. Mechanistic studies reveal that the process proceeds through an iron-mediated radical fluorine transfer process.

Non-canonical amino acids are important building blocks in the synthesis of natural products, peptides and drugs. Now, a one-pot chemoenzymatic approach to synthesize branched azacyclic non-canonical amino acids is reported. This method combines enzymatic transamination of 2,n-diketoacids and stereocontrolled chemical reduction to provide the desired products with high stereoselectivity.

The controlled growth of thin films of conjugated metal–organic frameworks is reported using an on-liquid-gallium surface synthesis strategy under chemical vapour deposition conditions. The surface flatness of the thin films is a tenfold improvement compared with samples synthesized by traditional routes.

A series of molecular rare-earth telluride clusters incorporating a three-centre, four-electron, tri-tellurido ligand (Te₃⁴⁻) are reported. These atomically precise clusters, possessing ultralow band gaps comparable to those of monocrystalline silicon and gallium arsenide, are potentially applicable as quantum materials and for optoelectronic applications.

Spontaneous reactions proceed thermodynamically downhill, limiting transformations to those that are exergonic. Now a chemically fuelled endergonic synthesis is reported in which a Diels–Alder reaction is driven uphill by a ratchet mechanism.

An efficient molecular nanojunction photocatalyst for hydrogen evolution is identified from a combinatorial molecular library, assisted by a materials acceleration platform, which is then scaled-up to the litre scale using flow synthesis.

Three closely related proline-based ligands give rise to different catalytic systems in asymmetric dialkylzinc addition reactions. Mechanistic studies reveal that monomeric, dimeric and product–catalyst complexes and aggregates larger than dimers are all catalytically active.

Control of atoms with single-atom precision is a key challenge in nanoscience. Now an electron beam approach to engineer shielded metal atoms in transition metal dichalcogenides is proposed. This method can create diverse atomic vacancies, leading to interesting magnetic and electronic properties.

Multicomponent catalytic reactions that generate enantioenriched boronic esters are underdeveloped. Now an N-heterocyclic carbene–nickel catalyst promotes enantioselective alkene 1,2-carboboration to access multifunctional alkylboronates, bearing a tertiary or quaternary β-stereocentre.

Radical-mediated synthesis of N-glycosides is underdeveloped. Here a glycosyl radical-mediated N-glycosylation reaction using combined copper and photoredox catalysis is reported. This protocol exhibits high chemoselectivity and water tolerance, overcoming challenges associated with cationic glycosylation reactions.

A navigation and positioning strategy is proposed for the scalable synthesis of a series of heteronuclear dual-atom catalysts via irradiation. It is shown that photo-induced electron accumulation at the M₁ site can attract an M₂ metal cation, forming heteronuclear dimers with high purity.

A chemist-intuited atomic robotic probe is developed that enables autonomous site-selective manipulation of magnetic nanographenes with atomic precision and aids in reaction mechanism elucidation through the incorporation of learned knowledge and artificial intelligence, leading to the intelligent synthesis of these materials.

The enantioselective folding of a planar nanographene layer is achieved in three steps: introduction of chiral information, enantiospecific ring closing with the removal of oxygen atoms and an enantiospecific Scholl reaction. The Scholl reaction introduces a helical bend in an all-carbon bilayer nanographene.

The development of strategies to access boronate esters from ubiquitous aliphatic C−H bonds is of long-standing interest in the synthesis community. Now a photoelectrochemically driven C(sp³)−H borylation reaction of alkanes is developed, in which iron, an abundant earth-based resource, is employed as a photoelectrochemical catalyst.

Precipitation of target functional materials from water is sensitive to precursor selection and aqueous electrochemistry (pH and redox potential), where competition between thermodynamics and kinetics can yield undesired impurity phases. Now, a theoretical framework to identify optimal synthesis conditions of target materials is developed and validated against a literature dataset and direct experiments.

Enzymatic C–Se bond forming reactions are rare. Now an enzymatic method for the synthesis of organoselenium compounds is reported using an ‘element engineering’ strategy. This method allows selenium analogues of cysteine, thiamine and a chuangxinmycin derivative to be produced using sulfur carrier proteins.

Alkane carbonylation through photocatalytic alkyl radical addition to CO is a challenge. Now, an equilibrium-leveraging strategy which combines the direct carbonylation of alkanes with CO with onwards enantioselective transformations is reported, providing an enantioselective method for the synthesis of β-amino and α-amino ketones.