Articles in 2024

Heteroatom-substituted C(sp³)-rich polycyclic hydrocarbon rings, isosteric to heterocyclic rings, are not common due to the challenging synthesis. Now a photoredox-catalysed strategy to insert amidyl radicals into bicyclo[1.1.0]butanes is presented, providing direct access to 2-oxa-4-azabicyclo[3.1.1]hept-3-enes.

The replacement of palladium with other metal catalysts in C–C bond-forming reactions is attractive in terms of costs and sustainability. Now an iron-based catalyst is successfully employed in the Suzuki cross-coupling of aryl chlorides with aryl boronic esters activated with tert-butyl lithium.

Achieving atomic control during the synthesis of heterogeneous catalysts remains challenging. Here the authors tackle this challenge by applying a liquid-phase atomic layer deposition approach to the synthesis of Cu/ZrO_x clusters on MgO as efficient catalysts for CO₂ hydrogenation to methanol.

Fe-exchanged zeolite catalysts are known for their ability to remediate NO_x and N₂O emissions, but their reactivity in mixed streams of NO and N₂O remains unclear. Now a suite of operando spectroscopies reveals the active Fe species involved in the process and their synergistic effect during the simultaneous conversion of these pollutants.

The catalytic activation of alkyl amines as α-nitrogen carbanions is challenging. Now the activation of N-arylidene-protected alkyl amines as carbanions by chiral ammonium organocatalysis for asymmetric conjugate addition and the Mannich reaction is reported, affording chiral α,α-dialkyl amines.

The catalytic power of DNA polymerases for artificial genetic polymer (XNA) synthesis remains underdeveloped. Now, the evolution and structure of an α-l-threofuranosyl nucleic acid polymerase is described that achieves XNA synthesis with ∼1 nt s⁻¹ and >99% template-copying fidelity.

The electrocatalytic activity of metal catalysts commonly exhibits a positive linear correlation with the presence of steps, but this dependency breaks down for Pt catalysts with high step densities. Now, using in situ electrochemical scanning tunnelling microscopy, it is shown that this is due to the bunching of closely spaced steps, forming double and triple steps.

Methanol selectivity is uncommon among CO₂ reduction electrocatalysts. A notable exception is the cobalt phthalocyanine catalyst supported on carbon nanotubes, yet the mechanism is still poorly understood. Now, two studies use a variety of analytical approaches to investigate the mechanism of the process including the role of alkali cations.

Traditional heterogeneous catalytic processes primarily hinge on the reactivity of solids. Now, a liquid metal catalyst based on a Cu–Ga binary system with dynamic structure and intriguing properties opens up an alternative for the conventional Haber–Bosch process for ammonia synthesis.

A photodiode can trigger bias-free redox reactions but is often hindered by thermodynamic barriers. Now, a bacteria-conjugated silicon biophotochemical diode allows simultaneous conversion of various carbon molecules with high efficacy.

Electrochemical nitrate reduction to ammonia is a promising approach for waste conversion, yet the use of a concentrated supporting electrolyte creates a product separation issue. Now, a porous solid electrolyte reactor with a cation shielding effect is reported for nitrate wastewater treatment and the production of pure ammonia.

Electrifying the fragmentation of hydrocarbons is an emerging challenge in the context of decarbonizing the chemical industry. To this end, competing electrocatalytic C–C cleavage and oxidation pathways of butane were investigated.

The merger of photocatalysis and transition metal catalysis has broadened the scope of chemical reactivity in organic synthesis. This Review provides an overview of the use of metallaphotoredox catalysis for sp³ C–H functionalizations that occur via single-electron, rather than hydrogen atom transfer.

The mechanism of electrocatalytic CO/CO₂ reduction on Cu surfaces is complex and its various mechanisms remain under debate, including the important role of cations in the electrolyte. Here the authors quantitatively determine the impact of alkali cations on the thermodynamics of CO adsorption under electrochemical conditions and the activation parameters of the rate-determining step.

Heterologous expression of an active, metallocentre-containing nitrogenase in a non-diazotrophic host is challenging. Now, the heterologous biosynthetic pathway of Mo-nitrogenase is pieced together in Escherichia coli using genes from Azotobacter vinelandii and Methanosarcina acetivorans.

The traditional Haber–Bosch process as well as recent alternative approaches based on photo- or electrocatalysis all rely on solid catalysts to convert nitrogen into ammonia. Here the authors disclose an effective method for the synthesis of this crucial commodity based on a Cu–Ga liquid metal catalyst instead.

The electrochemical reduction of CO₂ on organometallic catalysts is commonly limited to two-electron products. Now, an iron tetraphenylporphyrin catalyst immobilized onto a nickel electrode is shown to achieve a Faradaic efficiency for ethanol of 68% due to the strong electronic coupling between the catalyst and the support.

Sulfilimines are a class of chiral molecules that bear S(IV) stereocentres, which are of high value in drug discovery but difficult to synthesize. Now the authors report a chemo- and enantioselective Chan–Lam S-arylation of sulfenamides with arylboronic acids that delivers diaryl and alkyl aryl sulfilimines.

Recently, the pyridoxal-5′-phosphate-dependent enzyme SbzP was reported to catalyse a [3+2]-annulation reaction yielding β-NAD-derived antibiotics. Now, cryo-electron microscopy structures of a stable homologue and computational simulations provide structural and mechanistic insights into this enzymatic reaction.