Articles in 2023

Biocatalytic strategies typically transform only one alkene isomer into products, limiting the yield. Now a biocatalyst is reported to convert both isomeric silyl enol ethers into chiral α-branched ketones with high efficiency and excellent selectivity.

Arabinogalactan RN1 displays potent anti-pancreatic-cancer activity; however, the structure–activity relationship of RN1 is unclear. Now the synthesis of RN1 and a library of glycans are reported, using an iterative preactivation-based one-pot glycosylation strategy. Biological analysis reveals that a decasaccharide is the active structural domain of RN1.

A macroscale scaffolding strategy for building arches and curved surfaces is translated to the molecular level for the face-selective design of zeolitic metal–organic frameworks (ZMOFs).

Synthesizing phase-pure, higher-quantum-well thickness (n) 2D halide perovskites is challenging. Now, a general method, termed kinetically controlled space confinement, to synthesize 2D perovskites is reported. Transformation from low n-values to high n-values is achieved by tuning the temperature or time of crystallization.

β-Lactone-containing natural products are rare. Now, a polyketide with a unique cyclopentane–β-lactone skeleton is reported. The key enzymes identified for the formation of the bicyclic core are a non-ribosomal peptide synthetase-like module with a β-lactone ring forming esterase and peptidyl carrier protein, thioester reductase and condensation domains.

Direct conversion of air to nitric acid occurs under ambient conditions using a cathodic hetero-homogeneous electrocatalysis strategy.

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.

Catalytic enantioselective synthesis of all-carbon quaternary stereocentres is a long-term challenge in organic synthesis because of substantial steric repulsion and dissimilarities between the substituents around the stereocentre. This Review presents how the desymmetrization strategy plays an important role in constructing these types of motifs.

Unravelling the formation of binary nanocrystal phases is challenging. Here, by combining in situ small-angle X-ray scattering and molecular dynamics simulations, we show that AlB₂ and NaZn₁₃ superlattices undergo classical homogeneous nucleation consistent with the presence of short-range attractive interactions guiding the crystallization process.

In this approach, metal–organic framework (MOF) glasses are synthesized by the desolvation of mononuclear metal complexes. The MOF glasses are composed of transition metals and either carboxylate, pyridyl or azolate ligands. Their porous structures and formation of monoliths are regulated in this process.

Palladium-catalysed dicarbonylation using two different nucleophiles enables the selective synthesis of unsymmetrical diamides and amido esters in a single step.

High-entropy alloys (HEAs) have interesting properties, but the synthesis of uniform HEAs is challenging. Here design principles are established for the synthesis of core–shell nanoparticles, which can be thermally annealed to produce uniform HEA nanoparticles in a predictable manner.

The selective synthesis of non-symmetrical diamides and amido-esters is a challenge. Now a Pd-catalysed dicarbonylation method is reported that generates non-symmetrical diamides and amido-esters through diamino- and amino-alkoxy carbonylations of propargylic acetates using two different nucleophiles. Mechanistic studies reveal that the process occurs through a sequential carbonylation process.

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.

Arynes are often generated using strong bases or fluoride sources, limiting functional group tolerance. Now, stable triaryloxonium salts are transformed into arynes and subsequently trapped using cycloaddition reactions by treatment with potassium phosphate at room temperature. This functional group-tolerant method proceeds by an elimination, unimolecular, conjugate base-like elimination mechanism to form the aryne.

While enzyme-mediated oligosaccharide synthesis is versatile, it is often limited by the availability of glycosyl transferases. Now a chemoenzymatic strategy is reported, comprising enzymatic assembly of a core oligosaccharide followed by chemical manipulations, to produce a library of glycans that reveal binding specificities of serum antibodies.

Centring structure-directing agents govern structure assembly to consistently obtain sodalite topology backbone, yielding more than 20 isoreticular zeolite-like metal–organic frameworks with tailored pore apertures and porosity.

Performing enantioselective photocatalytic reactions with visible light is a challenging task that has seen substantial advances with the development of new catalysts. Although many approaches utilize dual-catalytic systems in which the photocatalyst is separate from the chirality-inducing moiety, in this Review bifunctional photocatalysts that perform both roles are discussed.