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Unstrained aryl–aryl bonds are among the most inert bonds in organic chemistry. Now the development of a split cross-coupling strategy enables the direct functionalization of such bonds through Rh-catalysed C–C cleavage and cross-coupling with aryl halides, providing a method for biaryl synthesis.
The synthesis of well-defined heterostructure interfaces can be leveraged to design advanced catalysts. Now a catalyst consisting of carbon-supported Janus particles with crystalline Ru and amorphous CrOx sides is shown to achieve high performance for both alkaline hydrogen oxidation and evolution reactions due to the synergy between both sides.
The electrochemical synthesis of ammonia via the lithium-mediated reduction of N2 holds great promise to replace the carbon- and energy-intensive Haber–Bosch process. This Review discusses this approach and examines the critical role of the catalytic solid–electrolyte interphase formed on the electrode.
The coenzyme Q biosynthetic pathway has evaded full characterization for decades, in part due to the inherent insolubility of coenzyme Q and the instability of its membrane-associated biosynthetic enzymes. Now, researchers have resurrected an active ancestral coenzyme Q metabolon in vitro that has unveiled valuable insights into previously uncharacterized aspects of coenzyme Q biosynthesis.
A deeper understanding of reaction mechanisms should lead to improvements in the selectivity of organic electrosynthesis methods. This approach has now been used to explain the role of magnesium diacetate in the Ag-electrocatalysed reductive coupling of sp3 organic chlorides with aldehydes or ketones with increased selectivity for the desired alcohol product.
Correlating structure and activity is a very important research goal in catalysis. This Editorial reflects on this topic, taking inspiration from examples in the current issue.
In 2018 a descriptor was put forward to correlate the activity of various electrocatalytic reactions on carbon-based single-atom catalysts, but some data the work was based on were later found to be incorrect. This work revisits and amends the original 2018 study while presenting a modified version of the φ descriptor.
Catalytic conjunctive cross-coupling for the generation of densely functionalized sp3-rich scaffolds that are often found in biologically active compounds is underdeveloped. Now, iron-catalysed dicarbofunctionalization of olefins with dialkylzinc and haloalkanes provides access to synthetically challenging C(sp3)-rich molecules.
Mucins are glycosylated proteins with important biological functions such as protection. Although glycopeptidases can cleave them, dedicated hydrolytic enzymes specific for mucins were unknown. Now microbial mucinases are discovered that specifically recognize mucin O-glycan clusters and employ two glutamic acid residues for catalytic cleavage.
The reasons for epistasis, wherein mutations interact non-additively, are often not fully understood. Now it is found that shifting the rate-limiting step from substrate binding to the chemical reaction step during the directed evolution of β-lactamase correlates with epistasis.
[Cu(phen)(binap)]+ features a relatively high photocatalytic activity, but its low photostability hinders its use in organic chemistry. Now immobilization of this motif on a metal–organic framework matrix enhances its stability and excited-state lifetime, enabling the promotion of [2+2] cycloadditions of styrenes with a variety of olefins, including electron-deficient alkenes.
Electrochemical cross-electrophile coupling with alkyl halides for the construction of C(sp3)–C(sp3) bonds is generally limited to activated alkyl halides. Now this approach is extended to coupling of unactivated alkyl halides using a nickel catalyst under mild conditions.
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.
The electrochemical synthesis of organic acids is often performed in alkaline electrolytes. This Analysis presents a techno-economic analysis highlighting the challenges involved in using such electrolytes for downstream product separation and electrolyte recovery.