Attractive phosphorus: Phosphorus atoms coordinated to up to nine neighbors can be found in the host structure of the clathrate Ba8M24P28+δ, which results in a new 22-vertex polyhedron (yellow). The physical properties can be tuned by adjusting the amount of phosphorus incorporated in the host framework of this new cage compound.
Remote control: New strategies for the activation of remote C(sp3)−H bonds by photoredox-catalyzed (PC) radical translocation via O- and N-centered radicals have recently been described. These methods enable the controlled and site-selective functionalization of inert C(sp3)−H bonds and provide new opportunities for reaction design (HAT=hydrogen atom transfer).
Ice-T loves nacre: An ice-templating approach resulted in a series of high-performance lamellar composites. This novel bioinspired approach opens up new opportunities for the preparation of bulk composite materials with tunable nano- and microscopic structures and various constituents.
Covalently binding molecules are frequently regarded as being generally promiscuous. In a recent study, binding selectivities and cellular target proteins of a wide variety of reactive fragments are examined in a proteome-wide context.
How fast are flashes? The field of flow chemistry has recently received increasing attention owing to the availability of commercial flow equipment. New syntheses with very short-lived intermediates have been enabled by sub-millisecond mixing and reaction regimes in tailor-made flow devices.
Versatile C−H insertions: Novel protocols for metal-carbene insertions using diazo compounds have been recently developed. Application of the respective rhodium and palladium catalytic systems allows formation of new carbon–carbon bonds in very good yields and selectivities.
Radical style: Several breakthroughs have recently been achieved in enantioselective C(sp3)−H functionalization through radical activation. These new strategies show how radical chemistry can be used to convert alkanes into functionalized chiral molecules (see scheme; HAT=hydrogen atom transfer).
Together forever? Functional selection was applied to finally achieve separation of the analgesic properties of opiods from serious side effects such as potentially lethal respiratory depression. A Gi-biased μ-opioid-receptor agonist (PZM21) was identified that stabilizes previously unexplored receptor conformations. This compound relieves pain in mice without causing hypoventilation or addiction.
Luminescent network: Colloidal excimer superstructures with unique optical and electronic properties have recently been described. Ground-state gold cluster cores were held together by the hydrogen-bonding network formed by their capping ligands, which enabled excimer formation.
In the beginning…: The Nobel Prize in Chemistry 2016 goes to three of the pioneers of the field of synthetic molecular machines, Jean-Pierre Sauvage, Sir J. Fraser Stoddart, and Ben L. Feringa. Their work has led from the reliable synthesis of rotaxanes and catenanes (see picture) to molecular rotary motors, shuttles, muscles, and other devices.
Got your work cut out: Stacking, cutting, and folding have been demonstrated to be a viable approach for the fabrication of robust nanocomposites from large-area graphene films and polymers. This method opens up an effective route towards strong, durable, and multifunctional nanomaterials with fascinating properties.
Red blood cells have been counted in an electrochemical collision experiment recently described by Compton and co-workers. As a cell collides with the electrode it lyses and a current is observed from the reduction of oxygen from within the cell.
Upgrading myoglobin with iridium: A metal-substitution strategy has been used to afford a repurposed myoglobin for challenging cyclopropanation and intramolecular C−H activation reactions. The performance of the iridium-loaded myoglobin (orange sphere) was improved through directed evolution of eight active-site residues (yellow surface).
The hydrogenation of CO2 to methanol is a potential process for the sustainable production of synthetic liquid fuels. The Cu/ZnO catalyst employed for this reaction has been studied extensively for many years, and recent progress now has the potential to turn it into a prototype for complex promotional interactions in heterogeneous catalysis.
Methods have recently been developed for the synthesis of excavated alloy nanoparticles. However, various challenges still need to be overcome for a broad range of excavated nanoparticles with different sizes, surface structures, compositions, and constituent elements to be available for chemical and energy transformations through thermal catalysis and electrocatalysis.
Exploiting the concept of iminium ion catalysis led to the discovery of the first organocatalytic Cope rearrangement of 1,5-hexadiene-2-carboxaldehydes. A diazepane catalyst exhibited optimal catalytic efficiency and offers possibilities for chiral modification.
There may be more than one way leading to RNA: Recent discoveries in the synthesis of nucleoside and nucleotide precursors are described and put into the wider context of prebiotic systems chemistry. Mixing Butlerow's carbohydrate precursors with Traube's 5-formylaminopyrimidines has led to the formation of prebiotic purine nucleosides whereas the mixing of 5-phosphoribose with barbituric acid and melamine gave supramolecular fibers from stacks of Whitesides’ rosettas.
Find your path: Methyl-coenzyme M reductase (MCR, turquoise) reversibly catalyzes the reduction of methyl-coenzyme M (methyl-S-CoM) with coenzyme B (CoB-SH) to form methane and the heterodisulfide. Recently, spectroscopic methods were used to detect trapped intermediates in a stopped-flow system, and CoM-S-NiII was identified after half a turnover of the MCR reaction (F430=nickel porphinoid). This finding supports a methyl-radical catalytic mechanism.
A rarely used element: The chemistry of ligand-stabilized complexes in oxidation state zero was recently extended to the s block with the discovery of a Be1 complex stabilized by a cyclic (alkyl)(amino)carbene. Combined experimental and theoretical studies provided conclusive evidence that the complex contains beryllium(0).
The power you're supplying: With the application of an optimized electrochemical approach, the allylic oxidation of olefins, which is an important C−H activation process that provides access to enones, becomes a sustainable, versatile, and potent key reaction for organic synthesis.
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