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The structure of core–shell catalysts is often assumed to be conserved over a reaction. Now, an in situ study reveals that the shell of Ni@Au nanoparticles is reversibly converted into a Ni–Au alloy during CO2 hydrogenation, with important mechanistic implications.
Nonlinear effects in catalysis have been shown to allow for asymmetric amplification. Here the authors report a particularly intriguing case whereby a catalytic asymmetric reaction gives a significantly higher product e.e. when run with a non-enantiopure catalyst compared to the enantiopure version.
The high reactivity of open-shell alkyl radicals makes their use in asymmetric catalysis challenging. Here the authors report a catalytic enantioselective desymmetrizing reaction of alkyl radicals and diols, forming stereocentres at the reaction site and at sites remote from it.
Platinum nanoparticles have been neglected as a catalyst for acetylene hydrochlorination due to their limited activity. Here, the authors show that nanostructuring to the single-atom level renders platinum on carbonaceous supports a superior catalyst for this important industrial process.
There are very few methods for the organocatalytic aziridination of unactivated olefins. Here the authors report a simple ketone catalyst for the transfer of nitrogen to isolated carbon–carbon double bonds, with good substrate scope and in high yields.
The cross-coupling of C–H bonds with alcohols is a highly efficient route to ethers. Here the authors report such an oxidative coupling, by use of a radical relay to both promote hydrogen atom transfer and activate the copper catalyst for cross-coupling.
The photocatalytic decarboxylation of fatty acids affords alkanes under mild conditions, albeit with limited selectivity due to radical-mediated side reactions. Now, a hydrogenated Pt/TiO2 catalyst is introduced for the selective conversion of C12–C18 fatty acids into Cn–1 alkanes in quantitative yields.
Supported single atoms can minimize metal utilization in catalysis, although reactivity restrictions exist. Here, fully exposed Pt, Pd and Rh ensembles localized on CeO2 islands anchored onto partially reduced γ-Al2O3 are introduced as a superior and durable alternative for three-way catalysis.
Abiological catalytic components can increase the synthetic potential of enzymes. This work reports an enzyme with two different abiological catalytic moieties—an organocatalytic unnatural amino acid and a metal complex—that act synergistically to achieve highly enantioselective Michael addition reactions.
Despite its potential, catalytic dry reforming of methane has not yet reached practical application due to high thermal energy requirements. Now, a photocatalytic method is introduced based on strontium titanate-supported rhodium nanoparticles that afford syngas production solely under light irradiation.
Bicyclo[1.1.1]pentanes are of interest to the pharmaceutical and chemical communities, due largely to their metabolic stability and potential as bioisosteres. Here the enantioselective C–H activation of these carbocycles is reported, giving access to enantioenriched, substituted products while maintaining the carbocyclic framework.
To implement more sustainable processes in industry, a high efficiency of microbial biocatalytic systems for the production of industrial chemicals from renewable feedstocks is important. Now, engineering the lifespan of Escherichia coli is presented as a platform technology for improving the bioproduction of chemicals.
Forming carbon–carbon bonds at the expense of two C–H bonds is difficult, but attractive, as it reduces the number of chemical steps during synthesis by avoiding prefunctionalization. Here such a method is reported, involving an interrupted Pummerer reaction and a photoredox-catalysed coupling.
Efficient microbial production of medium-chain fatty acids (MCFAs; C6–C12)—valuable molecules in the oleochemical and biofuel industry—is challenging due to their cellular toxicity. Now, this work improves the production of extracellular MCFAs to over 1 g l−1 by systematically engineering yeast at multiple levels.
Dry reforming of methane can so far afford syngas with equimolar CO and H2, which is suboptimal for Fischer–Tropsch chemistry. Now a process is reported based on a Ni–In molten metal alloy catalyst that is capable of producing syngas with practically relevant H2/CO ratios together with separable carbon.
The organocatalysed addition of aldehydes to nitroolefins is an extremely well-studied reaction that almost exclusively provides the syn-configured products. Here a general method to reverse the diastereoselectivity is reported, whereby a tripeptide catalyst consistently provides the anti product with high selectivity.
Amide reduction via hydroboration is challenging, and catalysts often exhibit limited substrate scope. Here the authors report synthesis of a lanthanum cluster as a catalyst for the hydroboration of esters and amides, capable of reducing a wide range of primary, secondary and tertiary amides to amines.
In order to use early, non-noble transition metals in homogeneous catalysis, complex ligands are typically needed, offsetting the benefits of inexpensive metals. Here the authors show that a simple manganese complex can be used in the hydrogenation of N-heteroarenes, without the need for additional ligands.
Electrochemical 2e− water oxidation is a promising route for renewable H2O2 production but it suffers from low selectivity due to the competing 4e− process. Here the authors demonstrate an interfacial engineering approach where the catalyst is coated with a hydrophobic polymer to confine in situ produced O2 and promote the 2e− pathway.
Investigation of proximity-driven enzyme regulation in intracellular signalling could benefit from suitable model systems. This work reports the engineering of a synthetic DNA origami-based apoptosome facilitating detailed analysis of caspase-9 activation, which is essential in programmed cell death.