Browse Articles

Enzymes catalyse radical-mediated fluorine atom transfer reactions for enantioselective C(sp³)-F bond formation.

Photocatalysts are crucial to diverse applications, but a challenge is the simultaneous and efficient delivery of photogenerated charges and mass to the catalytic sites. Now, through the systematic design of the skeleton and pores, a covalent organic framework is developed for the efficient photosynthesis of hydrogen peroxide using only water, air and light.

High-index facet nanostructures are deliberately targeted and synthesized by using a data-driven approach that integrates high-throughput density functional theory calculations, machine learning and experimental validation. The effectiveness of this approach is shown by the discovery and subsequent synthesis of seven monometallic and four multimetallic tetrahexahedron-shaped high-index facet nanoparticles.

The rational design and synthesis of dual-atom catalysts with structurally uniform and flexible active sites remains challenging. Now the tailored synthesis of a Janus Fe–Co dual-metal catalyst is reported in which the Fe and Co atoms are coordinated to N and O, respectively, and linked through bridging N and O atoms.

An unstrained allylic C(sp³)–C(sp³) bond is transformed into a new C(sp³)–C(sp³) bond enantioselectively with palladium catalysts via kinetic resolution or dynamic kinetic asymmetric transformation (DYKAT). Mechanistic experiments and density functional theory calculations reveal that the deracemization needed for DYKAT occurs via the formation of diene intermediates.

Palladium can be stabilized in the zero-oxidation state with one, two or three anionic aluminium ligands to produce mono-, di- or trianionic complexes, respectively. The palladium centres in the resulting complexes are highly negatively charged, and this electron richness enables the trianionic complex to undergo a hitherto hypothetical oxidative addition reaction with a diboron species.

Automated iterative small-molecule synthesis has generally been limited to around one carbon–carbon bond-forming step per day. Now, a next-generation automated synthesizer enables rapid, automated, iterative synthesis of a variety of small molecules. Improvements to chemistry and automation leads to a tenfold decrease in reaction time over previous automated platforms.

The electrochemical construction of C–N bonds from abundant CO₂ and nitrogenous sources is of interest for the sustainable synthesis of value-added organonitrogen compounds, which requires comprehensive considerations of electrocatalysts, the interface microenvironment, mechanisms, reactors and paired reactions to push this area towards competition with traditional thermochemical methods.

Electrochemical methods have great potential to help achieve net-zero emissions. Here, a method to synthesize ethylene carbonate is reported, which is electrochemically initiated and enables the concurrent production of hydrogen, capture of CO₂ and subsequent conversion of the captured CO₂ during ethylene carbonate synthesis.

Exploring artificial photosynthesis with water, air and light is a challenging goal. Here, a donor–acceptor porous framework photocatalyst enables efficient production of hydrogen peroxide from aerated water under ambient conditions.

Carbon-based fuels and value-added chemicals can be produced sustainably using electrochemical CO₂ reduction (CO₂R). This Review examines the expansion of scope through the coupling of CO₂R with heteroatomic co-reactants.

Geometry control in organic reactions can be used to promote dynamic processes or stabilize reactive transition states. This Review discusses the concept of geometry control, its impact on transition states and bonding, as well as the reactivity and properties that emerge as a consequence of constraining molecules.

The synthesis, isolation and characterization of palladium complexes featuring one, two and three anionic aluminium ligands are reported, in which the aluminium ligands effectively stabilize the palladium in the zero-oxidation state. The aluminium–palladium bonds are highly polarized and the negatively charged palladium centre readily undergoes activation of B–B and C–N bonds.

A one-pot method is introduced for synthesizing highly reactive and potentially chiral low-valency Ga(i) complexes, facilitating their application as a versatile catalyst.

An artificial metalloenzyme based on streptavidin with a biotinylated Rh(III) cofactor provides enantioselective access to various isoindolones with different functional groups. Rational engineering of the streptavidin scaffold reverses the stereoselectivity, offering an enantiodivergent method for the synthesis of isoindolones.

A high-symmetry tetrahedral cage made using smaller tripodal cages at its four vertices shows a high surface area for CO₂ and SF₆ adsorption.

A diazapentadienyl radical featuring a disubstituted carbon centre is discovered allowing the isolation and structural characterization of a stable secondary carbon radical.

The isolation of secondary and primary carbon radical species is challenging, owing to their instability. Now the reduction of an acyclic bis(imino)carbene conjugate acid enables the isolation of a stable pentadienyl-type radical. In silico and in vitro probing of its properties reveal a propensity to act as a secondary carbon radical.

Biocatalytic methods for the synthesis of isoindolones, via C–H activation, have remained elusive. Now, an enantiodivergent artificial-metalloenzyme-catalysed method for the synthesis of chiral isoindolones is reported, using a streptavidin–biotin–Rh(III) catalyst system. Crystallographic analysis reveals the key residues that control stereoselectivity in streptavidin.