Prochiral silanes: Recent work has demonstrated the powerful potential of enantioselective desymmetrization catalyzed by transition‐metal complexes in the stereoselective formation of silicon‐stereogenic silanes. These methods offer new possibilities for asymmetric synthesis of any functionalized chiral silanes that possess tetraorganosilicon stereocenters.

Good as gold: Gold hydrides were long considered unstable. In the past few years reports have appeared on not only the stable NHC gold(I) monohydride complex 1 (see structure; NHC=N‐heterocyclic carbene) but also a dinuclear gold(I) hydride and most recently the gold(III) monohydride complex 2 with a C‐N‐C pincer ligand. One can expect new and important impulses for inorganic and organometallic chemistry and homogeneous gold catalysis.

The origin of the charge on oil/water interfaces that can be found from electrokinetic mobility measurements is a long‐standing issue that has invoked different explanations. Sum frequency scattering (SFS) shows that impurities are likely not a general cause for the charge (see picture).

The effect of fatty acid impurities on the electrophoretic mobility of hexadecane in water emulsions is reinterpreted, occasioned by an error in the surface charge attributed to the fatty acids. The results are consistent with a surface charge contributed by both hydroxide ions and deprotonated fatty acids (see picture).

Pure is uncharged: Uncontaminated hydrophobic interfaces, such as PMMA‐H/water interfaces, are uncharged. If the macromolecules have instead ionizable carboxylic acid endgroups, such as PMMA‐COOH, a surface charge similar to the contaminated oil/water interface is obtained.

A new age dawned when 22‐year‐old William Lawrence Bragg (see picture) realized that the observations of X‐ray diffraction by a crystal can be interpreted very simply as arising from the reflection of the X‐rays by planes of atoms in the crystal. In the 100 years since this insight X‐ray diffraction has transformed chemistry, mineralogy, metallurgy, and, most recently, biology.

Essential: The discovery of vitamins was a scientific breakthrough that changed the world! The synthesis of vitamins on a commercial scale and their application in diets had a dramatically positive impact on human and animal health as well as economic development. The key achievements in research of vitamins are highlighted in this Review, starting from the first industrial synthesis of L‐ascorbic acid up to modern catalytic methods.

Antibody profiling: Native mass spectrometry analysis of intact antibodies can be achieved with improved speed, sensitivity, and mass resolution by using a modified orbitrap instrument. Complex mixtures of monoclonal antibodies can be resolved and their glycan “fingerprints” can be profiled (see picture). Noncovalent interactions are maintained, thus allowing antibody–antigen binding to be measured.

The two faces of gold: The reduction of oxygen on gold electrodes in alkaline solutions has been investigated theoretically. The most favorable reaction leads directly to adsorbed O₂⁻, but the activation energy for a two‐step pathway, in which the first step is an outer‐sphere electron transfer to give solvated O₂⁻, is only slightly higher. d‐band catalysis, which dominates oxygen reduction in acid media, plays no role. The reason why the reaction is slow in acid media is also explained.

C₆Br_six & drugs! C₆Br₆ can be used as the cooxidant/catalyst modifier for the [Rh^IIICp*]‐catalyzed (Cp*=C₅Me₅) dehydrogenative cross‐coupling of benzamides with simple benzene derivatives (see scheme, DG=directing group). Similarly, heterocycles can be coupled and druglike structures formed. Mechanistic studies suggest a unique and multiple role of the Cu(OAc)₂/C₆Br₆ system and a nonchelate‐assisted CH activation as the rate‐determing step.

Carbon anions in solution: C₂²⁻ dumbbells are well‐known in solid‐state compounds. The crystallization of the title compounds now shows that acetylide ions are existent in solution and therefore chemistry with small dissolved carbon anions may be within reach.

A positive effect: The bis(allyl)bismuth cation (see picture) in [Bi(C₃H₅)₂(thf)₂][B(C₆H₃Cl₂)₄] is superior to neutral tris(allyl)bismuth in the additive‐free allylation of unsaturated C‐heteroatom functionalities and the controlled living radical polymerization of activated olefins.

Reversible as well as stereo‐ and chemoselective: Various proteases such as thermolysin and chymotrypsin catalyze amine acyl exchange in peptides. This acyl exchange can be used to modify amino‐functionalized surfaces under physiological reaction conditions and provides an alternative mechanism for posttranslational transpeptidation reactions such as peptide‐splicing reactions in the proteasome.

Now even terminal: The 2,4,6‐trimethylbenzylidyne complexes [MesCM{OC(CF₃)₂Me}₃] (M=Mo, W) were synthesized from [Mo(CO)₆] and [W(CO)₆], respectively. The molybdenum complex is an efficient catalyst for the metathesis of internal and terminal alkynes and also for the ring‐closing metathesis of internal and terminal α,ω‐diynes at room temperature and low catalyst concentrations.

Separated: 3‐Hydroxy‐3‐phenylisoindolin‐1‐ones have been resolved by dynamic preferential crystallization. The compounds were effectively racemized through ring‐opening and ring‐closing reactions via achiral intermediates under basic conditions. Crystallization from a toluene solution containing 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) with stirring and evaporation of the solvent gave optically active crystals quantitatively with high ee values.

Go for the gold! Incorporating a borate anion into the backbone of a triphosphenium cation produces a unique zwitterionic phosphanide that can coordinate to one or two {AuCl} fragments depending on the steric bulk of the ligand (see picture; Au yellow, P purple, Cl green). Computational investigations show that in this μ‐type ligand, the phosphorus atom behaves only as a σ,π donor.

Ring ring: Annulated cyclohexenes were synthesized by using the title reaction with the cationic rhodium(I)/(R)‐H₈‐binap complex as a catalyst. In this catalysis, regioselective insertion of the acrylamide into a rhodacyclopentene intermediate and the coordination of the carbonyl group of the acrylamide to the cationic rhodium center suppress the undesired β‐hydride elimination.

Spring loaded: The smallest members of a family of carbon nanocoils (CNCs), adopting a fixed helical structure, have been synthesized by introduction of one or two staples in o‐phenylene ethynylene oligomers. The chiroptical responses of the systems having enantiopure L‐tartrate‐derived staples confirmed the induced helicity. Theoretical studies suggest that these CNCs are pseudoelastic.

Two birds with one stone: The simultaneous production of two important bulk chemicals, methanol and ethylene glycol, from CO₂ and ethylene oxide has been achieved under mild conditions by the highly efficient homogeneous catalytic hydrogenation of ethylene carbonate in the presence of a (PNP)Ru^II catalyst (see scheme).

Like a miniature trophy, the complex pictured was obtained as the sole product from the reaction of Sc₂C₂@C_3v(8)‐C₈₂ and [(μ‐H)₃Re₃(CO)₁₁(NCMe)] and characterized by IR, visible/near‐infrared, and NMR spectroscopy, mass spectrometry, and X‐ray diffraction. Coordination of the Re₃ cluster to the unique hexagon oriented perpendicular to the C₃ axis of the fullerene core altered the geometry and electronic properties of Sc₂C₂@C_3v(8)‐C₈₂.

Textbook revision: Allylboronic acids, which are easily prepared from allylic alcohols, react readily and selectively with ketones without Lewis acid catalysts.

Room for expansion: An efficient, regioselective, and convergent method for the ring expansion and rearrangement of 1‐sulfonyl‐1,2,3‐triazoles under rhodium(II)‐catalyzed conditions is described. These denitrogenative reactions form substituted enaminone and olefin‐based products (see scheme). The enaminone products can be further functionalized to give various heterocycles and ketone derivatives, thus rendering the sulfonyl triazole traceless.

O₂ in, H₂O out: Various diamines and related bisnucleophiles readily undergo oxidative isocyanide insertion with Pd(OAc)₂ (1 mol %) as the catalyst and O₂ as the terminal oxidant to give a diverse array of medicinally relevant N heterocycles. The utility of this highly sustainable method is demonstrated by a formal synthesis of the antihistamines astemizole and norastemizole.

The key step in this total synthesis of (−)‐acetylaranotin is the efficient formation of the characteristic dihydrooxepine ring from cyclohexenone through an unusual vinylogous Rubottom oxidation and a regioselective Baeyer–Villiger oxidation. (−)‐Acetylaranotin is obtained in 22 steps from commercially available L‐Cbz‐tyrosine (Cbz=benzyloxycarbonyl).

Revised: The total synthesis of gomerone C results in revision of the stereochemical assignment at C3 (see scheme). The synthetic strategy relies on a late‐stage Conia‐ene reaction, which efficiently forms the bicyclo[3.2.1]octane containing the bridgehead chloride and generates an exocyclic olefin, which can be used as a flexible handle for further elaboration. The two contiguous quaternary centers are installed by means of a Diels–Alder reaction.

Acid brings the oxygen: A general method for palladium‐catalyzed CH oxygenation has been developed for the facile synthesis of a wide range of functionalized phenols with readily available aryl ketones, benzoates, benzamides, acetanilides, and sulfonamides. A trifluoroacetic acid/trifluoroacetic acid anhydride solvent system serves as the oxygen source and is the critical factor for CH activation.

Ketone in charge: A formal ketone‐directed palladium‐catalyzed ortho‐hydroxylation of arenes has been developed as an effective approach to access o‐acylphenols from simple arylketones. A Pd‐catalyzed oxidative ortho‐carbonylation reaction using ketone directing groups to access a ketal–lactone motif is also demonstrated. The ubiquity and versatile nature of ketones make these methods attractive. BTI=PhI(TFA)₂; DCE=1,2‐dichloroethane.

Fluorishing: The Togni reagent allows efficient synthetic access to fluorine‐labeled RNA molecules (see picture). These are in turn highly useful for NMR spectroscopic analyses of secondary and tertiary structures, RNA–protein interactions, and functionality of riboswitch modules.

Linked: A method based on thiol‐ene chemistry enables the synthesis and purification of ubiquitin oligomers with ≥4 units. This approach, which employs free‐radical polymerization, can be applied towards the synthesis of homogeneous Lys6‐linked ubiquitin oligomers currently inaccessible by enzymatic methods. By using these chains, one can study their roles in the ubiquitin proteasome system and the DNA damage response pathway.

When Alpha met Beta: A tuneable α—β surface phase junction on Ga₂O₃ can significantly improve photocatalytic overall water splitting into H₂ and O₂ over individual α‐Ga₂O₃ or β‐Ga₂O₃ surface phases. This enhanced photocatalytic performance is mainly attributed to the efficient charge separation and transfer across the α–β phase junction.

The frog prince with his two identities pales in comparison with the shape‐shifting barbaralyl cation, which exists as a mixture of 181 400 degenerate forms. Gold‐catalyzed cycloisomerizations of 7‐alkynyl cyclohepta‐1,3,5‐trienes were found to proceed via fluxional barbaralyl intermediates (see scheme). The evolution of the intermediates into 1‐ or 2‐substituted indenes could be controlled by the choice of gold complex.

High‐level calculations: The Zimmerman di‐π‐methane rearrangement of dibenzobarrelene occurs via a triplet state to form dibenzosemibullvalene, overcoming two barriers connecting two biradicals. The shape of the triplet potential‐energy surface shows that the rearrangement involves two transition states. The first triplet diradical intermediate may bypass in the passive of the alkene triplet to the final intermediate (see picture).

The electrode‐specific formation of polydopamine films is achieved by applying positive voltage to the target electrodes at pH 6.0. The functionalization of the films is simultaneously carried out by co‐depositing dopamine with molecules of interest onto the electrode.

Singly twisted Möbius antiaromatic [34]heptaphyrin A and doubly twisted Hückel aromatic [34]heptaphyrin B were formed by a phosphorus insertion reaction. A rearranges thermally to give the more stable B with PO migration from NNN to NNC, and thus A is a rare case of a kinetically controlled Möbius antiaromatic molecule.

Giving directions: Optically active dihydropyrans bearing three contiguous stereogenic centers can be efficiently prepared by the title reaction. High stereo‐ and regiocontrol can be achieved by employing a bifunctional H‐bond‐directing aminocatalyst.

A golden opportunity: The total structure of a Au₃₆(SR)₂₄ nanocluster (see figure) reveals an unexpected face‐centered‐cubic tetrahedral Au₂₈ kernel (magenta). The protecting layer exhibits an intriguing combination of binding modes, consisting of four regular arch‐like staples and the unprecedented appearance of twelve bridging thiolates (yellow). This unique protecting network and superatom electronic shell structure confer extreme stability and robustness.

Encaged! Three‐terminal interlocked molecular species were obtained by dynamic (2+3) assembly of a cagelike macro‐bicycle around a trifurcated trispyridinium π guest. The complex is stabilized by π–π interactions and multiple [CH⋅⋅⋅O] and [CH⋅⋅⋅N] interactions. Uncomplexed guest molecules cocrystallize alongside the threaded complexes in the solid state, thus giving extended π‐stacked columns.

Metal‐mediated secondary structures of peptide‐based foldamers were constructed using artificial backbone‐coordinative oxime peptides. Complexation of the peptides with Pd^II afforded several mononuclear and dinuclear secondary structures such as helices and hairpins as confirmed by single‐crystal XRD and NMR analyses (see picture).

PET friendly: Labels for PET imaging are incorporated into completely organic porphysomes by using a fast (30 min), one‐pot, high‐yielding (>95 %) procedure to produce highly stable (>48 h) radiolabeled nanoparticles that show the highest specific activity ever reported for a ⁶⁴Cu‐labeled nanoparticle. These ⁶⁴Cu‐porphysomes can be accurately and noninvasively tracked in vivo.

Single‐protein‐chain superhelical filaments are obtained from monomeric repeat proteins by controlling the chemistry and solvent exposure at their terminal interfaces. The assembly was achieved in aqueous solution, at neutral pH value, and at room temperature. The building block was a recombinantly engineered designed tetratricopeptide repeat protein. Directed head‐to‐tail self‐assembly was driven by genetically encoded orthogonal native chemical ligation.

Frankenstein′s peptide: The grafting of the binding domain from miniprotein Min‐23 into the sunflower trypsin inhibitor (SFTI‐I) peptide scaffold (see scheme) preserved its in vitro and in vivo binding specificity and proteolytic stability. The combination of these peptides was shown to be tumor‐specific with a good binding affinity for delta‐like ligand 4 (Dll4) protein. The use of SFTI‐I as a peptide scaffold is ideal for hit‐to‐lead development.

At the surface of Aβ_1‐40 amyloid fibrils that have a threefold molecular symmetry (green in the left picture) a site of interaction of the glycosaminoglycan analogue heparin (blue) was identified. The binding site consists of residues at the N terminus and the turn regions defining the apices of the triangular geometry. Heparin has a lower affinity for Aβ_1‐40 fibrils having twofold molecular symmetry, thus revealing a remarkable morphological selectivity.

Pause and play: Dihydrooxazine oxides are stable intermediates that are protonated directly, without the intermediacy of the zwitterions, in organocatalytic Michael additions of aldehydes and nitroalkenes (see scheme, R=alkyl). Protonation of these species explains both the role of the acid co‐catalyst in these reactions, and the observed stereochemistry when the reaction is conducted with α‐alkylnitroalkenes.

Ion‐transport paths: Combined modeling and neutron diffraction studies provide atomic‐scale insights into Li₂FeP₂O₇, a material proposed for a new lithium‐battery cathode with reversible electrode operation at the highest voltage of all known Fe‐based phosphates. The results indicate that Li⁺ ions are transported rapidly through a 2D network along the paths shown in green in the picture.

An open and shut case: Photoirradiation of the 9‐mesityl‐10‐methylacridinium ion, which acts as a photoredox catalyst, evoked catalytic cycloreversion of the photochromic 1,2‐dithienylethene (DTE) compounds with one order of magnitude enhancement in quantum yields. Mechanistic studies revealed that the back electron transfer and electron transfer from the neutral closed form of DTE compounds to the open‐form radical cation are key steps.

Drop it! A highly enantioselective catalytic cascade reaction of α‐ketoacids and aldehydes is achieved using the title catalyst and water as the solvent. Fluorescence imaging shows that the catalyst is mainly distributed on the surface of emulsion droplets. Optically active isotetronic acids can be obtained with this method and the emulsion droplets are responsible for the high reactivity and enantioselectivity.

A simple and inexpensive approach is used to coat metal oxide surfaces (SBA‐15) with thin films of carbon. These carbon films provide improved hydrothermal stability to oxides, such as silica and alumina, which are not otherwise stable at elevated temperatures in the presence of liquid water (see picture). Furthermore, the carbon film changes the surface chemistry of the support.

Recharging spent BN fuel: {Cr(CO)₃} mediates the reduction of borazines by hydride and methyl nucleophiles to generate anionic complexes of dearomatized hexamethylborazine. Subsequent quenching leads to the release of a substituted cyclotriborazane, successfully demonstrating the stepwise reduction of a BN bond.

Caught in the act: Imaging mass spectrometry of a button mushroom (see picture) infected with the soft rot pathogen Janthinobacterium agaricidamnosum in conjunction with genome mining revealed jagaricin as a highly antifungal virulence factor that is not produced under standard cultivation conditions. The structure of jagaricin was rigorously elucidated by a combination of physicochemical analyses, chemical derivatization, and bioinformatics.