Articles in 2022

Alternaric acid is a known starting point for herbicide development. Now, the development of a total synthesis enables structure–activity relationship profiling of compound libraries, which, combined with phenotypic screening and molecular modelling, identifies lead compounds with enhanced herbicidal activity compared with alternaric acid.

Chemical reagents readily oxidize alkyl amines at sites adjacent to nitrogen. Achieving selective oxidation at specified non-adjacent sites is much more challenging. A computation-guided process is introduced that enables rapid optimization of enzymes for site-selective hydroxylation of a variety of cyclic amines.

Developing highly elastic and conductive hydrogels is challenging, especially for use in harsh environments including organic solvents and extreme temperatures. Now, a self-assembly and in situ polymerization method is reported for the fabrication of highly compressible and environmentally adaptive conductive hydrogels with concrete-type constituents and high-tortuosity interconnected cellular architectures.

The complexity of carbohydrate structures makes their synthesis challenging. Now, an automated glycan synthesizer is reported which is capable of preparing a library of bioactive oligosaccharides, including a fully protected fondaparinux pentasaccharide. Furthermore, the synthesizer can rapidly assemble arabinans up to 1,080-mer size, starting from monosaccharide building blocks.

Two-dimensional materials have many desirable properties but controllable synthesis is difficult. Now, a flux-assisted growth approach has been designed to reproducibly prepare high-quality, atomically thin materials. Eighty atomically thin composite flakes have been prepared by this approach.

Degradable polymers are needed to overcome the environmental persistence of the materials. Now, cyclic–acyclic monomers metathesis polymerization is reported to produce degradable thermoset, thermoplastic and elastomeric polymers. The material properties and degradability of the polymers are investigated after different treatment methods during their synthesis.

Selective oxidation of ring C–H bonds is an attractive route to functionalized cyclic amines, which are versatile intermediates in drug synthesis. Now, engineered P450 enzymes, designed with computational guidance to disfavour undesired products, are reported to oxidize all unactivated C–H bonds in cyclic amines with high selectivity.

Coordination of a photoswitchable chiral phosphate ligand to an achiral manganese(iii)-salen complex yields a catalyst that can produce either enantiomer of an epoxide from a single alkene substrate. This enantiodivergent catalysis is governed by the transfer of the chirality of the phosphate ligand to the manganese(iii)-salen complex.

Methods for electrochemical recycling of microplastic waste to value-added products are extremely sought-after. Here, a tandem photoelectrochemical-bioelectrocatalytic approach converts microplastics to chemical fuels and uses the microplastics as an electron source for electrochemical transformations.

β-Hydride and β-heteroatom eliminations are competitive processes in many Pd-catalysed reactions but general strategies for controlling this selectivity have not been established. Now, a mechanistic study of Pd-alkyl complexes demonstrates that the choice of phosphine ligands and leaving groups controls selectivity.

Bifunctional catalysts containing metal and acid sites are used industrially in alkane hydroconversion. Now, the nanoscale spatial separation of the two active sites is shown to promote hydroisomerization and inspires design principles for this type of catalyst.

Developing a bench-stable glycosyl donor of multifunctional sugar residues that can be activated under mild conditions is a challenge in carbohydrate chemistry. Now, stable glycosyl sulfones are used in a photoinduced method for desulfonylative cross-coupling to prepare a range of C- and S-glycosides.

Developing enantiodivergent catalysts capable of preparing both enantiomeric products from one substrate in a controlled fashion is challenging. Now, a manganese(III)-salen complex with a chiral photoswitchable phosphate counterion is reported for the epoxidation of alkenes in a stereoselective manner, where irradiation with light allows access to either enantiomer of the epoxide.

Plastic waste poses a serious economic, ecological and environmental threat. Here, non-recyclable, post-consumer microplastics are used as an electron feedstock for biosynthetic reactions in a photoelectrocatalytic system. The microplastics are simultaneously broken down into organic fuels, meaning that this system provides valuable chemicals at both the anodic and cathodic sites.

β-hydride and β-heteroatom eliminations are elementary steps in many catalytic reactions used in the synthesis of drug molecules and polymers. However, the elimination processes often compete leading to unpredictable outcomes. Here, a series of mechanistically informed selection rules are developed to selectively achieve the desired elimination.

Using anion-binding interactions to tackle challenging polymerizations is an ambitious goal and in its infancy. Seleno-cyclodiphosph(v)azanes are demonstrated to exert anion-binding interactions to precisely control the equilibrium between a dormant covalent precursor and active cationic species under mild conditions, thus enabling living cationic polymerization.

The four editors making up the launch team of Nature Synthesis outline their key topics of interest within the scope of the journal.