Research articles

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.

The synthesis of high-nuclearity copper(I) nanoclusters remains challenging due to their low stability. Now four high-nuclearity Cu(I) nanoclusters have been successfully isolated by introducing a bifunctional phosphoramide ligand into the Cu/RC≡CH assembly system, enhancing complex stability through cooperative bonding.

The catalytic carboxylation of C(sp²)–H bonds using CO₂ is an efficient strategy to produce carboxylic acids; however, the carboxylation of azines is a challenge. Now, a visible-light-driven, thiolate-catalysed method for the carboxylation of azine C(sp²)–H bonds using CO₂ is reported, enabling the synthesis of N-heteroaromatic carboxylic acids with excellent regiocontrol.

The use of a universal chemical programming language (χDL) to encode and execute synthesis procedures for a variety of chemical reactions is reported, including reductive amination, ring formation, esterification, carbon–carbon bond formation and amide coupling. These procedures are validated and repeated in two international laboratories and on three independent robots.

Acid-triggered reversible addition–fragmentation chain-transfer polymerizations, in the absence of conventional initiating species and in the dark, are reported to prepare polymers with low dispersity and high end-group fidelity. The protonation of monomers catalyses both the initiation and propagation steps and can also be applied to free radical polymerizations.

Low-selectivity photocatalytic carbon dioxide reduction has been overlooked, due to the difficulty in separating and utilizing the mixed products. Now, a triple tandem strategy is reported to convert the mixed reduction products, H₂ and CO, sequentially into olefinic and carbonyl fine compounds with high atom utilization efficiency.

Homologation of organoboronates by iterative carbenoid insertion is an effective method for the synthesis of alkyl chains, but the corresponding homologation using vinyl units remains elusive. Now, a stereoselective vinylene homologation reaction is reported, comprising diastereoselective successive insertion of silyl- and alkoxy-substituted carbenoids into organoboronates, followed by a Peterson-type elimination.

Chiral α-quaternary amino and glycolic acids have found use in medicinal applications. Although their synthesis through α-alkylation is well known, synthesis via α-arylation remains challenging. Now, palladium-catalysed methods for the enantioselective α-arylation of amino acid- and glycolic acid-derived heterocycles, azlactones and 5H-oxazol-4-ones, using aryl bromides, are reported.

The use of gaseous sulfuryl fluoride in sulfur(VI) fluoride exchange reactions is a challenge. Now, a flow set-up for the on-demand generation and onward reaction of sulfuryl fluoride, from sulfuryl chloride, is reported. The process produces fluorosulfate and sulfamoyl fluoride analogues of small molecules, peptides and proteins.

Water electrolysis can produce clean hydrogen, but it is limited by the slow anodic oxygen evolution reaction. Now, a local electronic manipulation strategy for stabilizing high-valence Ru single site catalysts has been developed. The catalyst demonstrates efficient bifunctional activity for water electrolysis.