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Methane has been notoriously difficult to activate for useful chemistry. Now, a tandem catalyst system comprising an iron-modified zeolite and an enzyme is developed for the partial oxidation of methane to formaldehyde under ambient conditions using hydrogen peroxide as the oxidizing agent. This approach achieves high selectivity and conversion to formaldehyde.
A catalytic, metal-free method for generating carbanion equivalents has been developed, providing a modern alternative to classical Grignard addition reactions. This approach overcomes the traditional drawbacks associated with the use of stoichiometric amounts of metalated reagents, aligning this strategy with contemporary sustainability requirements.
Conventional thermocatalytic routes to 1,3-butadiene are energy intensive. Now, a method for the selective electroreduction of acetylene to 1,3-butadiene under ambient conditions is demonstrated. Use of an iodide-containing electrolyte stabilizes partially oxidized copper sites on the catalyst, facilitating the synthesis of 1,3-butadiene with a Faradaic efficiency of up to 93%.
Understanding metalloenzymes can inspire the design of molecular catalysts. Employing signal-enhanced nuclear magnetic resonance spectroscopy on parahydrogen-reduced [Fe]-hydrogenase, two reaction intermediates have been characterized. This work paves the way toward a microscopic understanding of these metalloenzymes.
Recent findings on electrocatalysis promoted by alkali metal ions (AM+) have challenged the prevailing consensus that AM+ are chemically inert spectators. Now, theoretical and experimental evidence of an AM+-coupled reaction intermediate contribute to confirming the catalytic role of AM+ in electrochemical processes.
Elucidating the nature of the Fe active sites in Fe-zeolite catalysts and the reaction mechanism operating during the concurrent removal of NO and N2O is very challenging. Now, complementary transient operando spectroscopies are deployed to disentangle the structure and activity of diverse Fe species and elementary reaction steps.
Photoredox catalysis is merged with metalloenzymatic catalysis to enable asymmetric decarboxylative azidation and thiocyanation. These transformations are achieved by coupling the photoredox activation of N-hydroxyphthalimide esters using a synthetic photocatalyst with enantioselective radical capture by Fe(iii) intermediates of non-haem iron enzymes.
Polymer/whole-cell hybrid catalysts were created by synthesizing catalytically active polymers from the surface of Escherichia coli cells that recombinantly expressed enzymes. The surface-engineered bacteria allowed for orthogonal tandem catalysis, involving photo- or chemocatalytic steps by the polymers on the cells and biocatalytic steps by the enzymes within the cells.
In the quest for more efficient and sustainable asymmetric catalytic methods, synthetic organic chemistry has relentlessly explored innovative techniques. This Comment highlights an emerging topic — photoelectrochemical asymmetric catalysis (PEAC) — which fuses molecular photoelectrocatalysis with asymmetric catalysis.
Biocatalysis needs improved reproducibility and quality of research reporting. Our interdisciplinary team has developed a flexible and extensible metadata catalogue based on STRENDA guidelines, essential for describing complex experimental setups in biocatalysis. The catalogue is available online via GitHub for community use.
Decarboxylative azidation is a valuable transformation in organic chemistry, but a biocatalytic equivalent remained elusive. Now merging photoredox with metalloenzymatic catalysis enables the enantioselective decarboxylative radical azidation and thiocyanation of N-hydroxyphthalimide esters.
Alkali cations in electrolytes are commonly considered chemically inert species, but their role has recently been called into question. Now, using in situ spectroscopy and molecular dynamics simulations, it is shown that alkali cations couple with intermediates in the oxygen reduction reaction, acting as cocatalysts.
Proton-exchange membrane water electrolysers often rely on scarce iridium or ruthenium catalysts at the anode, as many low-cost, earth-abundant catalysts cannot withstand the harsh operational conditions. This Review discusses the state of the art in earth-abundant water oxidation catalysts and examines their degradation mechanisms at multiple levels.
The catalytic mechanism of [Fe]-hydrogenases is not well understood. Now a signal-enhanced nuclear magnetic resonance method based on parahydrogen is introduced to study [Fe]-hydrogenase under turnover conditions in situ, revealing intermediates of the catalytic cycle.
Compatibility issues often limit chemoenzymatic systems. Now it is shown that the proximity between catalytic polymers grafted from the membrane of microorganisms and intracellular heterologous enzymes enhances the reaction rates of a photoenzymatic system, while the coating increases the stability.
The development of catalytic systems for sequestering anthropogenic methane emissions from the atmosphere could potentially reduce global warming. Now, coupling the enzyme alcohol oxidase with an inorganic zeolite generates formaldehyde from methane under ambient conditions with 90% selectivity.
The capability and importance of computational methods in organic chemistry is steadily increasing. This Review provides an overview of computational methods for the design of asymmetric catalysts, with the aim of avoiding specialist computational language to make the field more accessible to experimental chemists.
Despite the importance of difluoromethyl (CF2H)-bearing centres for pharmaceuticals, there is currently no general strategy for the stereoselective introduction of a CF2H group at chiral centres. Here the authors describe an enantioconvergent difluoromethylation method for racemic alkyl halides to construct such stereocentres.
