Research articles

The in situ generation of reactive (di)gallenes from a gallium–fluorobenzene complex and commercial chiral and achiral bisphosphine ligands is presented. The Ga(I) complex cations can undergo reversible cycloadditions to 1-alkenes and bond insertions into H–Si and H–B bonds.

Development of fluorine rebound processes at an enzymatic Fe(III) centre are a challenge. Now, a plant-derived non-haem iron enzyme, 1-aminocyclopropane-1-carboxylic acid oxidase, is repurposed and evolved to catalyse chemo- and enantioselective C(sp³)–H fluorination, forming a range of enantioenriched organofluorine products.

A computationally guided approach was used to predict the hierarchical assembly of four trigonal-shaped organic cage compounds into a more symmetric, higher-order, tetrahedral-shaped ‘cage of cages’ that crystallizes into a porous superstructure.

Enantioselective triple [2 + 2 + 2] cycloadditions are reported that enable the synthesis of 3D π-extended carbo[11] and [13]helicenes, which show excellent circularly polarized luminescence brightness (up to 513 M⁻¹ cm⁻¹), the highest value among helicene derivatives.

Renewable electricity-driven nitrogen oxidation is a green alternative to Haber–Bosch and Ostwald processes, but it is challenging to effectively steer oxygen intermediates towards the nitrogen oxidation reaction pathway. Now, to mitigate competing oxygen evolution and improve nitrogen oxidation efficiency, the use of hydroxyl radicals as the nitrogen oxidant is proposed.

Atomically thin gold nanosheets are predicted to have interesting properties but their synthesis is challenging. Here the exfoliation of two-dimensional single-atom-thick gold, termed goldene, is achieved through wet-chemically etching Ti₃C₂ from Ti₃AuC₂. The synthesized goldene has promising properties as a heterocatalyst.

The controlled degradation of larger and potentially harmful molecules into smaller, and preferably valuable, products is a crucial step to close the waste–degradation–synthesis loop envisioned by circular chemistry. Now, a forward-synthesis algorithm is designed to facilitate such degradation-oriented analyses, and proof-of-concept experimental validation is provided.

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.