Reviews & Analysis

Monolayer gold could exhibit properties of benefit to various applications, but has been challenging to synthesize. Now, the exfoliation of two-dimensional single-atom-thick gold layers — termed goldene — is achieved through wet-chemically etching away Ti₃C₂ from Ti₃AuC₂, a nanolaminated MAX-phase. Goldene shows lattice contraction and an increase in the gold 4f binding energy compared with the bulk.

A strategy for the precise and scalable synthesis of a series of M₁M₂ (where M is a metal ion) heteronuclear dual-atom catalysts (DACs) is proposed. Photoinduced electron accumulation at the M₁ sites results in the capture and reduction of M₂ cations close to the M₁ sites to generate DACs with high purity.

The enantioselective synthesis of an inherently chiral molecular nanographene is demonstrated by precisely controlling the sequential generation of chiral elements in its structure. The final stereocontrolled graphitization step allows for the separate synthesis of both enantiomers, thus paving the way towards chirality controlled all-carbon nanographenes.

A general strategy for synthesizing high-nuclearity Cu(i) alkynide nanoclusters is developed, involving a tripodal polydentate phosphoramide ligand to stabilize the nanoclusters and an alkynol ligand for the facile in situ generation of the ethynediide (C₂^2–) dianion to template nanocluster formation. The Cu(i) alkynide nanocluster Cu62 exhibits good stability and activity as a catalyst for photobleaching.

The direct carbonylation of alkanes with CO suffers from low conversion owing to equilibrium constraints. Now, a strategy is presented that combines reversible alkane carbonylation with an asymmetric transformation to overcome the equilibrium limitations, enabling the synthesis of chiral β- and α-amino ketones from alkanes, CO and anilines.

The visible-light-driven thiolate-catalysed carboxylation of C(sp²)–H bonds in azines using CO₂ is demonstrated. This procedure can be applied to various azine substrates to obtain a range of N-heteroaromatic carboxylic acids with different functionalities, including bioactive molecules and carboxylated N-ligands.

Since the isolation of a Mg–Mg complex, research on low-oxidation-state s-block chemistry has flourished. An approach to forming metal–metal bonds between Mg and the heavier alkaline earth metals (Ca, Sr and Ba) is now demonstrated. The unusual electronic nature of these compounds could stimulate further discussions of metal–metal bonding.

Modular access to nimbolide could provide the opportunity to develop agents that target poly-ADP-ribose polymerase 1 (PARP1) for the treatment of BRCA-deficient cancers. Now, a convergent strategy is reported, in which late-stage coupling of a pharmacophore-containing building block and a diversifiable hydrazone unit enables the preparation of nimbolide and various analogues.

Rapid, long-distance transport of an ultrathin and uniform palladium film on a two-dimensional (2D) crystal of tungsten ditelluride at accessible temperatures is reported. The surprising effect is generalizable and offers possibilities for exploring chemical synthesis in nanoconfined spaces and access to not yet synthesized 2D materials.

An engineered ‘carbene transferase’ is shown to convert both Z and E isomers of silyl enol ethers in a stereoconvergent manner, yielding chiral α-branched ketones with high efficiency and excellent selectivity. This biocatalyst offers an efficient and high-yield method to functionalize these alkene mixtures.

A preactivation-based one-pot glycosylation strategy was used to synthesize RN1 — a polysaccharide comprising 140 monosaccharide units isolated from Panax notoginseng, as well as a glycan fragment library. Evaluation of the biological activity of the glycans in vitro revealed that a decasaccharide fragment shows anti-pancreatic cancer activity.

A β-lactone compound — globilactone A — has been discovered through genome mining and heterologous expression of a biosynthetic gene cluster. Biosynthetic investigations unveiled the mechanism of the formation of the cyclopentane-β-lactone core.

Design principles are established for the colloidal synthesis of core–shell nanoparticles, which serve as precursors for the general and predictable synthesis of high-entropy alloy nanoparticles as monodisperse samples.

A chemoenzymatic strategy is introduced whereby a glycan backbone is assembled enzymatically to give a core oligosaccharide that is subjected to chemical manipulations to install terminal epitopes. A library of oligosaccharides containing the human natural killer-1 epitope was synthesized, enabling evaluation of the binding specificities of serum antibodies of patients with anti-myelin-associated glycoprotein neuropathy.

A strategy for the transition-metal-free C(sp²)−C(sp³) cross-coupling of α-(pseudo)halo aliphatic ketones and arylboronic acids via a 1,4-metallate shift is demonstrated. The reaction proceeds under mild conditions in the presence of base, and offers an operationally simple method for the construction of C(sp²)−C(sp³) bonds.

A strategy for the cobalt-catalysed allylic fluoroalkylation of terpenes can provide site-selective access to various fluorine-containing motifs under mild conditions. The extension of the protocol to a 2-mol-scale synthesis indicates the scalability of this method.

Chiral macrocycles are of interest for various applications, including drug discovery, but are challenging to synthesize. Now, a method for enantiocontrolled macrocyclization is demonstrated, involving the confinement of a linear substrate within a self-assembled chiral capsule. This method shows good substrate scope and affords chiral macrocycles with high enantioselectivities and conversions.

The most popular reactions used by medicinal chemists are often incompatible with nanoscale ultrahigh-throughput experimentation (ultraHTE). Now, a set of ultraHTE-amenable reaction conditions is reported for four of the most important transformations in drug discovery, and their generality and scalability tested on a range of complex natural products and drug candidates.

A mild and efficient electrochemical strategy has been developed for the multicomponent 1,4-arylalkylation, unsymmetrical dialkylation and hydro(deutero)alkylation of 1,3-enynes with aryl and alkyl bromides as cross-coupling partners. This protocol can be used to synthesize diverse allenes bearing various functionalities, including allenes found in natural products and drugs.

Cyclic iminium salts are used as versatile intermediates in the synthesis of diverse N-(hetero)aryl piperidines. This method facilitates the C2 and/or C3 functionalization of the piperidine backbone with motifs relevant to medicinal chemistry, enabling the exploration of previously inaccessible chemical space for the discovery of medicines.