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The direct cross-electrophile coupling of (hetero)aryl halides and pseudohalides is challenging. Now this reaction is facilitated by a visible light-induced palladium catalytic system that differentiates the reactants on the basis of the bond dissociation enthalpy affording unsymmetrical (hetero)biaryls.
S-formyl thiols can be produced by S-formylation reactions in enzymatic processes that fix CO2 through the formate dehydrogenase enzyme. Here the authors show the use of an organocatalytic metal-free process for the direct mono- and di-S-formylation of thiols using CO2.
Multiple parameters are generally responsible for the reactivity of particulate catalysts, although nanoparticle proximity is often neglected. Here the authors report the impact of such structural factor using the hydrogenation of benzaldehyde over PdAu nanoparticles supported on macroporous SiO2 as the probe reaction.
Photocatalytic H2O2 production from water and air is limited by the availability of these substrates and charge carriers at the catalytic sites. Here a donor–acceptor covalent organic framework acts as a supply chain for the delivery of charge, water and oxygen, resulting in 17.5% quantum efficiency under visible light irradiation.
C–H activation in organic chemistry usually relies on precious and toxic transition metals. Now it is reported that a sustainable photo-promoted iron-catalysed aromatic imine C–H alkenylation reaction with alkynes circumvents previous limitations of related iron-catalysed reactions that required additives or high reaction temperatures.
Chemoenzymatic cascade reactions are often hindered by catalyst incompatibility. Now, the co-packing of catalyst-loaded Pickering emulsion droplets and solid microspheres into a continuous-flow column reactor leads to efficient combination of homogeneous, heterogeneous and enzymatic catalysts.
Acetyl-CoA carboxylation is the canonical route for endogenous malonyl-CoA formation in cells. Here, the authors design a non-carboxylative malonyl-CoA pathway independent of acetyl-CoA into multiple microbes for efficient malonyl-CoA-derived natural products biosynthesis.
The mechanism by which bimetallic catalysts can outperform their monometallic counterparts is often unexplained. Now nitrate hydrogenation on bimetallic catalysts is shown to proceed via the electrochemical coupling of hydrogen oxidation and nitrate reduction half-reactions, each of which occurs on one metal component.
Axial chirality is a key element in many valuable compounds, such as ligands in organic chemistry or pharmaceuticals. Now the catalytic atroposelective synthesis of acyclic 1,3-dienes by chiral phosphoric acid-catalysed bromination is described, expanding the chemical space of axially chiral compounds.
Precious-metal-free catalysts for water oxidation commonly suffer from low stability in acidic electrolytes. Now, by controlling the intergrowth of the γ-MnO2 structure, it has been possible to achieve 2 A cm−2 at 2 V and a stability of over 1,000 hours at 200 mA cm−2 in a polymer electrolyte membrane electrolyser.
The generation of Fischer-type carbene complexes for organic synthesis usually requires stoichiometric amounts of metal. Now the palladium-catalysed formation of a Fischer-type carbene intermediate for the synthesis of β-lactam derivatives is described and its crystal structure is solved.
Single metal atom catalysts on N-doped carbon supports are promising materials to replace Pt as cathode catalysts in fuel cells. Now a transient voltammetry method is applied to extract the kinetic and thermodynamic parameters of the oxygen reduction reaction on an iron phthalocyanine model catalyst.
Fixing CO2 into value-added solid carbon such as carbon nanofibres is a promising process but poses substantial challenges. Now a tandem strategy is proposed where CO2 and water are electrocatalytically converted into syngas to subsequently form carbon nanofibres via a thermocatalytic process.
Ring-expanding carbon-atom insertion reactions are currently limited to the installation of few functional groups. Now researchers show the use of a radical carbyne precursor for the insertion of carbon atoms bearing varied functional groups to access 2-substituted naphthalenes from indene.
Heterogeneous catalysts are often dynamic under operation. Now, the mechanism of CH4 dry reforming on Ni is studied by in situ microscopy and spectroscopy, revealing the formation of metastable surface nickel–oxygen structures from CO2 dissociation that exhibit different catalytic properties and induce rate oscillations.
The electrochemical deoxygenation of carbonyl groups by hydrogenolysis is challenging as the competing hydrogenation usually prevails. Now the electrochemical Clemmensen reduction is proposed, achieving the selective hydrogenolysis of various carbonyl compounds using Zn as the electrocatalyst in a mildly acidic solution.
Photocatalytic overall water splitting on particulate systems represents a possibility for clean energy storage, yet efficiencies for the process are typically low. Here, highly concentrated saltwater is used to polarize photoexcited N-doped TiO2, resulting in enhanced charge separation and a solar-to-hydrogen efficiency approaching 20%.
Coenzyme Q has several important biological functions, but the understanding of the biosynthesis of coenzyme Q in humans remains incomplete. Now, by constructing the entire COQ metabolon in vitro, the enzymes and reactions underlying coenzyme Q biosynthesis are characterized.
The reconstruction of Cu electrocatalysts during CO2 reduction is an impediment to the stability of this technology, yet a clear picture of the species involved in this process remains elusive. Here, the authors demonstrate the presence of transient solution-based Cu(I) species and theoretically predict complexes with CO and oxalate as the likely candidates.
C–C bond formation involving sp3 centres has typically relied on stoichiometric reagents. Here catalytic Ag electrodes modified with Mg(OAc)2 enable electrocatalytic coupling of an organic halide with an aldehyde for the selective formation of a broad scope of alcohol products.