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Nickel complexes are of ever-increasing importance in organic synthesis; however, unstable Ni(COD)2 is still the main Ni(0) source used. Here the authors report a solution to this long-standing issue: an air stable Ni(0) complex that acts as a general precatalyst for numerous nickel-catalysed reactions.
Methods to allow access to all isomers of a product are both valuable and challenging to achieve. Here the authors report a catalytic system comprised of an N-heterocyclic carbene and an iridium complex, and show that it can be used for the asymmetric, diastereodivergent synthesis of γ-butyrolactones.
Additions to alkenes and alkynes are useful routes for generating highly functionalized products. Here the authors report the 1,1-difunctionalization of alkynes through a CuH-catalysed asymmetric hydroboration/hydroamination cascade.
The sugar d-apiose is important in plant cell wall polysaccharides. Here the authors elucidate the complex, multistep biosynthetic pathway for its production using enzyme crystal structures and computational analysis.
The synthesis of organophosphorus compounds from elemental phosphorus is an inefficient process, using multiple steps, stoichiometric metal complexes and/or hazardous reagents such as chlorine gas. Here, a direct photocatalytic route to convert white phosphorus (P4) into phosphines and phosphonium salts is reported.
The synthesis of chiral amines is of crucial importance for the pharmaceutical industry, but it remains a challenging task and is often inefficient. Now, a heterogeneous iridium complex is developed for the asymmetric hydrogenation of imines and the asymmetric reductive amination of carbonyl compounds in continuous flow with high yields and enantioselectivities.
The electrocatalytic upgrading of CO to higher-value feedstocks provides a promising route to multicarbon products. Here, the authors show that high ethylene selectivity can be achieved by constraining CO availability on copper, with an ethylene Faradaic efficiency of 72% and a partial current density of >800 mA cm−2.
The asymmetric hydrogenation of alkenes is a common route to optically active compounds, but alkene synthesis is often atom-inefficient, and the formation of isomers further complicates the procedure. Now the Ir-catalysed deoxygenation of racemic alcohols is shown to be a simple route to enantioenriched products.
Photocatalytic activation of alkyl carbon–chlorine bonds has constantly proven difficult due to the high energies needed to cleave this stable bond. Here a surfactant-based photocatalytic system is used, allowing for the radical dehalogenation and subsequent reactivity of unactivated alkyl chlorides.
Due to its stability nitrogen is often employed as an inert gas during catalytic reactions. Now, a study shows that N2 can act as promoter for the catalytic hydrodeoxygenation of p-cresol on supported ruthenium catalysts through the formation of hydrogenated nitrogen species acting as a source of protic hydrogen.
Deuterated molecules are important both as labelled probes and as targets in their own right. Here the authors report a very simple and general deuteration of aldehydes, by the use of an N-heterocyclic carbene catalyst in the presence of D2O.
This work shows that the biosynthesis of the polyether tetronasin involves an apparent enzyme-catalysed inverse-electron-demand hetero-Diels–Alder reaction to form an unexpected oxadecalin intermediate. A second enzyme then rearranges the oxadecalin to form the four-ringed tetronasin.
To achieve large-scale application of water electrolysers we need to find optimal cathode and anode catalysts. This work reports an engineered silver catalyst with high density of stacking faults that exhibits high activity and stability for the hydrogen evolution reaction, outperforming commercial platinum on carbon.
Lithium-ion batteries exhibit high theoretical gravimetric energy density but present a series of challenges due to the open cell architecture. Now, Zhou and co-workers confine the reversible Li2O/Li2O2 interconversion into a sealed cell by pre-embedding Li2O nanoparticles into an iridium–graphene catalytic host.
Visualizing catalysts at work poses significant experimental challenges. Here, an operando scanning tunnelling microscopy study of the cobalt-catalysed Fischer–Tropsch synthesis is presented, which establishes steps as the active sites of the process by correlating activity under realistic conditions with step density.
Selective functionalization of C(sp3)–H bonds is difficult in alkanes and other hydrocarbons, and especially so for enantioselective reactions. Here the authors report a photocatalyst and chiral metal catalyst to allow the radical, asymmetric addition of alkyl, allylic and benzylic groups to imines.
Reductive desymmetrization of 2,2-disubstituted cyclodiketones can provide valuable complex molecules with multiple chiral centres, but the generation of a single stereoisomer is difficult. This work addresses this synthetic challenge by engineering the activity and stereoselectivity of a carbonyl reductase.
Tackling the loss of expensive cofactors is a key challenge in continuous-flow biocatalysis. This work reports immobilized enzymes with a tethered cofactor that is channelled between a recycling and a catalysis module facilitating total turnover numbers of NAD+ and ATP exceeding 10,000 in biocatalytic flow systems.
Simple enzyme mimetics are highly desired for industrial settings providing high catalyst stability and low production costs. This work reports that phenylalanine and zinc ions can self-assemble into a supramolecular structure showing catalytic properties similar to those of the natural enzyme carbonic anhydrase.
Asymmetric routes for the formation of tetrasubstituted allenes are scarce and limited in scope. Now, a catalytic asymmetric process is reported giving access to tetrasubstituted allenes from readily available propargylic alcohols, and a potential role for an achiral supporting ligand is postulated.
Enantioselective synthesis of atropisomeric biaryls is highly desirable due to the utility of these compounds as ligands and catalysts. Now, an organocatalytic polyketide cyclization is shown to convert poly-β-carbonyl compounds into binaphthalene derivatives in good enantioselectivities.
Multi-modal approaches to simultaneously characterize different aspects of a reaction in situ are not readily accessible. Here, catalyst extrudates equipped with both luminescence thermometry and Raman spectroscopy sensors are introduced, providing an in-depth picture for the conversion of syngas on a supported rhodium catalyst.
Due to its importance, the water-gas shift reaction has been the subject of numerous studies; however, a unifying mechanistic picture has not yet emerged. Now, a combination of spectroscopic, kinetic and computational methods reveal the crucial role of carboxyl intermediate for this centuries-old process.
Small changes in catalyst synthesis can have large and often poorly understood effects on activity. Here the authors show how variation of post synthetic heat treatment—in combination with changes in metal loadings—can lead to the most efficient catalysts, and also identify the most likely active sites.
Imine reductases have been regarded as one of the most promising enzymes by the pharmaceutical industry—but their industrial application is still lacking. This work reports the successful industrial application of an imine reductase, enabled by directed evolution.
Directed evolution typically requires extensive screening. This work presents an ultrahigh-throughput microfluidic assay, based on a coupled reaction and fluorescence-activated droplet sorting, enabling a 960-fold activity improvement of an amine oxidase for a non-natural substrate in a single round.
One of the major challenges in C–H functionalization is to achieve selectivity when multiple bonds of similar reactivity are present. Now, a method to selectively amidate sterically and electronically similar β- or γ-C–H bonds that utilize different silver catalysts is reported, giving access to valuable 1,2- and 1,3-aminoalcohols.
Targeted therapy is an important approach to reduce the side effects of medicinal drugs. This work reports the synthesis of catalytically active Pd nanostructures in exosomes that selectively target cancer cells for drug activation using biorthogonal chemistry.
Cu2O is a promising photocatalyst, although its stability is compromised by a disproportionation reaction that leads to the formation of Cu and CuO. Now, a method is reported to stabilize Cu2O nanocubes, rendering them highly active and stable for the photocatalytic reverse water–gas shift reaction.
Here the enantioselective lithiation of Boc-1,3-oxazinanes is reported. Transmetallation to zinc allows for regiodivergent functionalization at either C4 or C5 positions via a ligand-controlled Negishi coupling, and subsequent oxidative cleavage gives easy access to both β2- and β3-amino acids.
Elucidating reaction mechanisms on electrode surfaces is of utmost importance. Now, using canonical transition state theory, Cuk and colleagues show the competing pathways by which the charge-trapping intermediates of the water oxidation reaction on n-SrTiO3 decay towards the next step in the reaction.
Performing photocatalytic CO2 reduction in a selective fashion with molecular catalysts represents a considerable challenge. Here, a binuclear cobalt complex featuring a bi-quaterpyridine ligand is developed that can selectively afford either carbon monoxide or formate by selection of the reaction medium acidity.
Traditional modes of catalyst deactivation such as Ostwald ripening and particle migration and coalescence eventually lead to sintering and particle growth. Now, Cargnello and colleagues identify loading-dependent particle decomposition into single atoms as an important deactivation mechanism during methane combustion on colloidal Pd nanocrystals.
α-Branched amines are commonplace in pharmaceutical agents. This work reports the synthesis of α-branched amines by simultaneous C–C and C–N bond formation at the sp3 carbon branch site through an 1,1-alkene addition pathway and utilization of three readily accessible starting inputs in a single catalytic cycle.
The direct amination of alcohols with ammonia is a modern and clean route for the synthesis of amines. This joint theoretical and experimental study reveals the key factors governing the activity and selectivity to primary amines on metals, which are then used for the rational design of bimetallic catalysts.
Encapsulation is an effective strategy to tune metal-catalysed reactions, although its potential has not been fully explored. Here, design principles and advanced understanding of the reactivity of different polymer-encapsulated Pd nanocrystals are provided using CO oxidation as a benchmark reaction.
The development of efficient and low-cost electrocatalysts for the oxygen evolution reaction is critical for improving the efficiency of water electrolysis. Here, the inactive spinel CoAl2O4 is activated via iron substitution to achieve high activity and stability for water oxidation.
C-aryl glycosides are present in many natural products and of interest in drug design, but their chemical synthesis is challenging. This work reports an efficient and diastereoselective ortho-directed C−H glycosylation of arenes and heteroarenes with glycosyl chloride using a palladium catalyst.
Efforts to harness the cellulolytic activity of enzyme assemblies have been mainly empirical due to the lack of quantification tools. Now this work reports experimental and theoretical approaches to quantify enzyme assemblies, revealing the parameters that are important for cellulolytic activity.
The synthesis of stereodefined alkenes is challenging, and often relies on the steric bias of the substituents. Here the authors report a photoredox/nickel catalysed difunctionalization of alkynes, giving access to either E- or Z-tri-substituted alkenes, depending on the photocatalyst used.
The production of high-value fuels from bio-derived methanol requires improvement to become economically viable. Here, process advancements for the production of high-octane gasoline are reported, and the effects that these have on making the process competitive with market rates of fossil fuels are analysed.
The synthesis of ethanol via CO2 hydrogenation is a challenging process, often hampered by low selectivity. This work reports a Zr12 cluster-based metal–organic framework as support for cooperative Cu(i) sites that catalyse CO2 hydrogenation to ethanol with remarkable selectivity upon promotion with caesium. Credit: Cloud background, CC0 1.0 Universal Public Domain Dedication.
Biocompatibility plays a crucial role for the development of artificial metalloenzymes (ArMs) for therapeutic applications. This work presents an ArM with a ruthenium catalyst that is protected from physiological glutathione and accumulates in cancer cell lines for metathesis-mediated prodrug activation.
The fleeting nature of transition state ensembles of protein motions has precluded their experimental observation. This work provides an atomistic insight into the rate-determining structural transition of adenylate kinase during catalysis by high-pressure NMR and molecular dynamics simulations.
Combining enzymatic and heterogeneous catalysts is challenging due to different reaction requirements. Here, a method is presented constructing single protein–polymer nanoconjugates as nanoreactors for the in situ synthesis of enzyme–metal nanohybrids with high activity at ambient conditions.
Regenerating expensive S-adenosylmethionine (SAM) in enzymatic in vitro reactions is challenging—but important for the commercial scope of SAM-dependent enzymes. This work reports a simple two-enzyme cascade for the in vitro regeneration of SAM for the enzymatic methylation of diverse substrates.
Metal oxide alloys are important industrial catalysts, but their structure–activity relationships are poorly understood. Now, a study encompassing a combination of computational tools and machine learning approaches sheds light on the activity and selectivity of zinc–chromium oxides during syngas conversion.
The roughness factor of an electrode has been generally used to increase total rates of production, though rarely as a means to improve selectivity. Now, Jaramillo, Hahn and co-workers direct the selectivity of CO reduction to multicarbon oxygenates at low overpotentials by increasing the roughness factor of nanostructured Cu electrodes.
The active sites of metal-free carbon catalysts for the oxygen reduction reaction remain still elusive. Now, Yao, Dai and co-workers combine work-function analyses with macro/micro-electrochemical measurements on highly oriented pyrolytic graphite and conclude that pentagon defects are the main active sites for acidic oxygen reduction.
Primary alcohols are known for their broad application in life sciences and the chemical industry. Now, Beller and colleagues present a regioselective, iron-catalysed hydrogenation of aliphatic and aromatic epoxides as a general route to primary alcohols under mild conditions