Natural(ly) fit: The X-ray crystal structure of the bacterial membrane protein MraY in complex with its natural product inhibitor muraymycin D2 is discussed. MraY catalyzes one of the membrane-associated steps in peptidoglycan biosynthesis and, therefore, represents a promising target for novel antibiotics. Structural insights derived from the protein–inhibitor complex might now pave the way for the development of new antimicrobial drugs.
Recent developments in catalytic carbonyl–olefin metathesis are summarized in this Highlight. Schindler and co-workers have reported that the environmentally benign FeCl3 catalyst promotes ring-closing carbonyl–olefin metathesis (RCCOM) in high yield under very mild conditions.
Coppercabana: The copper(I) hydride catalyzed functionalization of unactivated alkenes has been shown to be compatible with conventional carbonyl reduction. Through the combination of both pathways or complete suppression of C=O reduction in favor of C=C functionalization, methods for the stereoselective synthesis of a variety of chiral molecules have been developed.
Alkyl with alkyl: A significant development in alkyl–alkyl cross-coupling reactions, namely the nickel-catalyzed decarboxylative Negishi coupling of N-hydroxyphthalimide esters, was recently reported by Baran and co-workers. This method enables the synthesis of various highly functionalized compounds, including natural product derivatives.
Now within reach: In the remote C−H arylation of alicyclic amines the key step is the transannular coordination of the palladium catalyst (see picture, DG=directing group). This strategy is convenient for the late-stage functionalization of complex bioactive molecules in order to probe structure–activity relationships.
Spitting image: Herein a recent paper on the imaging of bioorthogonal groups using three-dimensional electron microscopy is discussed. The work has demonstrated electron microscopy imaging as a technique suitable for gaining structural information on bioorthogonal groups in their cellular context.
A large polycyclic hydrocarbon with a singlet biradical ground state has been obtained by the combined effects of topology and electron-accepting aromatic substituents, which stabilize its open-shell singlet state.
Ex machina: A computational method for predicting rate constants for reactions within microporous zeolite catalysts with chemical accuracy has recently been reported. A key feature of this method is a stepwise QM/MM approach that allows accuracy to be achieved while using realistic models with accessible computer resources.
Early transition metals are well known to catalyze the cleavage and functionalization of N2. In this Highlight, recent work showing that a rhenium catalyst is also capable of carrying out this difficult task is summarized, and a synthetic cycle for the stoichiometric incorporation of atmospheric N2 into acetonitrile is presented.
The combination of −I and −M effects and the aromaticity of the conjugate base renders the chiral pentacarboxy-substituted cyclopentadienes (PCCPs) acidic. Their convenient synthesis together with substrates derived from the chiral pool and their performance in the tested reactions renders them prodigious candidates to become a new and highly competitive class of chiral Brønsted acid catalysts.
All together now: Combination in a single reactor of the catalysts for converting syngas into methanol and methanol into olefins was recently reported by Cheng et al. This approach considerably simplifies the catalytic conversion of natural gas.
Losing contact: Omniphobic surfaces can be readily produced by acid-catalyzed graft polycondensation of dimethyldimethoxysilane (PDMS). Droplets show a very small contact angle hysteresis as well as a low sliding angle of only a few degrees. The nm-thick PDMS layer is neither easily washed away nor depleted. This method offers a novel approach towards the preparation of super-liquid-repelling surfaces.
Knitting: Recently Antonchick and Manna described a unique annulation that knits together three acetophenones to construct cyclopropanes. The cascade is mediated by organocopper and free radical species, and amounts to the first known [1+1+1] cyclotrimerization. It works well for ketones having electron-deficient or electron-rich substituents in their aryl rings. DTBP=di-tert-butylperoxide.
CSi electronics: Recently, Simon and co-workers demonstrated silicon-wafer-supported elastic carbide-derived carbons (CDCs) films without any delamination or cracks for micro-supercapacitor application. The fabrication of these CDC films is particularly important for the practical application of micro-supercapacitors in silicon-based electronics and flexible electronics.
One life, two strategies: Crucial structural differences between the human and the Plasmodium falciparum proteasomes were recently identified. A combination of cryo-EM and functional characterization enabled the design of a selective antimalarial proteasome inhibitor that shows low toxicity in the host. When used with artemisinin, this ligand offers a new approach for the efficient treatment of malaria at all stages of the parasite lifecycle.
Old cofactor, new tricks: In enzymes, coenzyme B12 has a well-known function as a radical initiator through homolysis of the Co−C bond. It has recently been shown that nature has repurposed this cofactor as a photosensitive switch for the regulation of bacterial carotenoid biosynthesis. Co−C bond breakage is again the key event in this process, triggering huge conformational changes in the B12-binding protein.
The construction of single-atom-thick sheets of boron on a silver substrate, which was published in late 2015, represents a significant advance towards the realization of useful two-dimensional materials based solely on boron. This Highlight provides background information on the topic of boron allotropes and an outlook for further work in this area.
Tied up in knots: The crystal structure of a DNA enzyme in its post-catalytic state was solved. The results provide insight into the structural possibilities for DNA and the mechanism of DNA catalysis.
Polar exploration: Recently, Linclau and co-workers disclosed a straightforward 19F-NMR method for determining the log P values of fluorocarbons. The method is particularly useful for most polar compounds and provides a quantitative way to rationalize the more subtle stereoelectronic consequences of fluorine introduction.
Old tricks, new dog: CRISPR/Cas9 is a powerful tool for gene editing that requires an endonuclease (Cas9) and RNA strands. It has been shown that chemical modification of the RNA structures, an approach that has been used to improve the efficiency of RNA interference, can also be applied to enhance the activity of CRISPR/Cas9 and reduce its off-target effects.
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