Linking two worlds: As a further expansion of the biocatalytic repertoire, carbene insertion into Si−H bonds catalyzed by the heme protein cytochrome c was recently reported. This new biocatalyst holds great promise because it enables the highly selective incorporation of silicon into molecules without prior protection of existing functional groups.

Inspiration–imitation–innovation: Parallel to the elucidation of the biological properties and physiological function of vesicles, increasingly elegant artificial vesicles are being reported. This Review provides an overview of the complex and rapidly developing fields of natural and synthetic vesicles and shows how the two fields can profit from one another.

7 Seconds, a geological timescale: The supercritical hydrothermal flow is a new method to produce phases, such as tobermorite, that are metastable under the synthesis conditions. Tobermorite is important in the construction industry. In contrast to traditional methods, reaction/crystallization takes just a few seconds and the product resembles much more closely the natural mineral tobermorite.

All in one and one for all: A one-pot sequence involving the iridium-catalyzed hydrosilylation of silyl esters and boron-catalyzed rearrangement enabled by-product-free siloxane-bond formation. Oligosiloxanes could also be synthesized in a single flask in a programmed fashion by a sequence of iridium-catalyzed hydrosilylation, boron-catalyzed rearrangement, and boron-catalyzed cross-coupling (see scheme).

In with Mn: The versatile title reaction sets the stage for fluorescence labelling and ligation of structurally complex peptides by synergistic catalysis under racemization-free conditions. A plausible catalytic cycle is proposed.

Defenses down: In the presence of a preformed biarylphosphine-supported palladium(II)–aryl complex and a weak base, lysine amino groups in unprotected peptides underwent C−N bond formation at room temperature (see scheme). The process was applicable to the conjugation of a variety of organic compounds, including complex drug molecules, to peptides and was also successfully applied to the formation of cyclic peptides through macrocyclization.

On target: Pyrimidine-based, template-assisted meta-C−H alkylation and alkenylation with allyl alcohols and protected allyl alcohols has been developed. Sulfonyl, carbonyl, and phosphonyl esters were used as linkers between the directing group (DG) and target meta-C−H bond of arenes.

An excellent chemoselectivity profile and a broad substrate scope characterize the title reaction, which contributes to expanding the rather limited portfolio of C−heteroatom bond formations via C−O functionalization. It can be applied to challenging substrate combinations and iteratively, which shows the prospective impact of this protocol in complex settings.

Let's get active: The title reaction of aryl silanes to deliver active hexafluoroisopropyl (HFIP) benzoate esters features high selectivity and good functional-group tolerance. This method yields products bearing two independently modifiable sites. NMR studies reveal the presence of hydrogen bonding between HFIP and a pyrimidine nitrogen atom of the directing group (DG), and it is thought to be crucial for the success of this alkoxycarbonylation reaction.

A trifluoromethylthio anion generated from a S₈/:CF₂/F⁻ system occurs by sulfuration of difluorocarbene rather than capture of difluorocarbene by fluoride. This process translates well to rapid trifluoromethylthiolation and [¹⁸F]trifluoromethylthiolation of α-bromo carbonyl compounds.

Pyridinium salts are formed in an organoselenium-catalyzed regioselective C−H pyridination of 1,3-dienes. The efficient C-2 selective method was successfully applied to direct C−H pyridination of alkenes. Fluoropyridinium reagents or initially loaded pyridine derivatives acted as pyridine sources in the pyridination reactions.

A general method for difluoromethylation of alcohols with difluorocarbene under weakly basic or acidic aqueous conditions by using TMSCF₂Br as a unique and practical difluorocarbene reagent is developed. This method is efficient for the selective synthesis of alkyl difluoromethyl ethers from functionalized alcohols, and a mechanism different from difluoromethylation of phenols is disclosed.

Odd couple: Treatment of a side-on dioxygen complex of cobalt with a low-valent cobalt or iron diketiminate complex affords a homobimetallic Co/Co or a heterobimetallic Fe/Co oxo complex, respectively. C−H activation in the Co/Fe complex is three orders of magnitude faster than in the homobimetallic analogue.

Reduction! Quinolines and related N-heteroarenes are hydrogenated using [Co]/L. The reactions proceed under mild conditions in a highly selective manner.

All together now: A highly selective cascade reaction for C−C/C−O bond formation through palladium-catalyzed oxidative carbonylation/carbocyclization/alkoxycarbonylation of enallenols was developed, affording spirolactones bearing an all-carbon quaternary center. Preliminary attempts to obtain enantioselectivity in the carbonylative carbocyclization revealed that the VAPOL-type chiral phosphoric acid serves as a good anionic co-catalyst in this transformation.

Iron sulfide (FeS_x) thin films were obtained by atomic layer deposition. Nanoscale FeS_x coatings on porous γ-Al₂O₃ powder were also prepared and showed excellent catalytic activity and selectivity in azobenzene hydrogenation.

Switching aromaticity: 1,3-Phenylene- and 2,5-thienylene-bridged [46]decaphyrins A and B have been synthesized. While A shows Hückel-aromatic character derived from its global 46π-conjugated circuit, B displays an (annuleno)annulene-type structure consisting of two twisted Möbius-aromatic thia[28]hexaphyrins. Upon protonation, these [46]decaphyrins undergo large structural changes and become strongly aromatic.

Introducing asymmetry: The iridium catalyst generated from [{Ir(cod)Cl}₂] (cod=cyclooctadiene) and a chiral P/olefin ligand facilitates the intermolecular asymmetric dearomatization of β-naphthols with allyl alcohols or allyl ethers. Highly functionalized β-naphthalenone compounds bearing an all-carbon-substituted quaternary chiral center were obtained in up to 92 % yield and 98 % ee.

Co-op: The cooperative dual-catalytic system of a chiral iridium complex and phosphoric acid achieves highly enantioselective allylic dearomatization reactions of naphthols with racemic secondary allylic alcohols. The desired β-naphthalenones, bearing an all-carbon quaternary center, were obtained in good yields. Both β-naphthalenone enantiomers can be obtained by simply employing opposite enantiomeric ligands.

How low can you go? Carbophilic gold carbenes derived from α-diazoesters react with enamides in an unprecedented aza-ene-type reaction. The presence of 0.1 mol % of a chiral Brønsted acid is sufficient to achieve excellent yields and enantioselectivities.

A designed β-hairpin phospholipid-inspired phosphopeptide crystallizes to form a lamellar structure that is stabilized by a variety of hydrogen-bonding interactions. The crystal structure together with ssNMR provide insight into the molecular arrangement within the self-assembled semi-elliptical nanosheets. The crystal structure could prove valuable for enhancing the predictability of intermolecular interactions for the design of self-assembling oligopeptides.

Age doesn't matter: Fully copper-exchanged high-silica LTA zeolites show unprecedented activity for selectively reducing NO_x with ammonia, even after hydrothermal aging at 900 °C. Si yellow, O red, Cu blue.

Like a seedpod: A soft device that mimics seedpod opening is described. Isomerization of a light-responsive molecular switch drives the twisting of liquid-crystal elastomer strips. As these strips twist in opposite directions, the pod eventually pops open from stress.

Running mild: A mild and selective insertion of a metal center into the arene ring is reported. The simple Cp*Ir fragment cleaves strong aromatic C−C bonds in alkylarenes without affecting weaker C−H and C−C bonds. This work reveals a conceptually new type of reactivity that could be important for a range of industrial processes involving the generation of chemicals and fuel from coal and plant biomass.

Polycyclic pentalenes with phenanthrene-type π extensions were prepared from 1,4-bis(bromoaryl)-1,3-butadiynes by successive transannular cyclizations of the in situ generated tetrakisdehydro[16]annulenes. These polycyclic pentalenes show not only high thermal stability, but also intriguing absorption and redox properties, due to the pronounced Hückel antiaromaticity.

Ylide meets B⁺: Employing a metalated ylide as donor ligand makes possible the isolation of highly stable ylide-functionalized boron cations. π-Delocalization as well as electrostatic interactions within the C−B−C linkage play the most important role for the high stability of the [Y−B−Y]⁺ cation and its Lewis base adducts. Reaction with amines results in N−H activation by addition across the B−C bond.

Stay in the saddle: A curved polycyclic hydrocarbon synthesized by extending the twisted bischrysene core by two indene units displayed a stable singlet biradical structure in the ground state. X-ray crystallographic analysis clearly revealed its saddle-shaped conformation.

Gel-like materials are formed when ultralight sponges made from short electrospun fibers are filled with solvent. These sponges offer numerous possibilities for new gel processing and design.

Missing, but not missed: Vanadium-doped FeOOH is a low-cost, highly efficient iron-based electrocatalyst for water oxidation without Ni or Co participation. It exhibits a low overpotential 390 mV (10 mA cm⁻² catalytic current density), low Tafel slope of 36.7 mV dec⁻¹, and a considerable durability.

Near and far: Spectroscopic and theoretical studies on the dynamic translocation process of countercations around a polyoxometalate–organic hybrid anionic molecular cluster show that electrostatic interactions and cation–π interactions regulate the position of small countercations around single clusters.

Throwing DARTs at a surface: The strain-promoted oxidation-controlled cyclooctyne-1,2-quinone cycloaddition (SPOCQ) between bicyclo[6.1.0]nonyne (BCN) and a surface-bound quinone revealed an unprecedented 100 % conjugation efficiency.

Unconventional Michael: The iminium ion activation of α,β-unsaturated aldehydes allowed stereoselective interception of photochemically generated hydroxy-o-quinodinomethane intermediates (A). The chemistry, which provides a direct entry into enantioenriched β-benzylated aldehydes, proceeds through an unconventional Michael-type addition path instead of a classical cycloaddition manifold. Computational studies have shed light upon the origin of this unexpected reactivity.

Clicking the immune system off: We report a method to rapidly reprogram the binding of sialic acid sugars on living cells to their cognate Siglec receptors through glycoengineering and click chemistry. Binding could be improved by more than 100-fold and in a selective manner. The modified cells showed potent immunosuppressive activity resulting from strong signaling through Siglecs on immune cells.

The old switcheroo: A kinetic and spectroscopic analysis of alkyne-dependent chemoselectivity in the copper-catalyzed azide–alkyne click (CuAAC) reaction is reported. Studies of six alkyne subtypes reveal that the rate-determining step (RDS) of an aromatic ynamine class is shifted from acetylide formation to the azide ligation/migratory insertion event allowing chemoselectivity independent of overall rate.

Cross-coupling meets amide bond formation: Decarboxylative cross-coupling with redox-active esters forms C−C bonds using boronic acids, organozinc, and organomagnesium species with simplicity comparable to amide bond formation. The extensive study enables selection of optimal activating agents and conditions across various substrates, including notoriously challenging heteroarenes.

Ch-ch-ch-changes: Guided by molecular dynamics calculations, chemical protein synthesis was used to explore the impact of allo-Thr and allo-Ile substitutions for individual Thr and Ile residues on the folding, crystal structure, and stability of the ShK protein. The experimental folding and thermal stability data matched well with the computational results.

Pent-up energy: A ruthenium-based water oxidation catalyst linked to porphyrin–fullerene units in a molecular pentad has been synthesized. Transient absorption indicated the photoinduced multistep electron transfer afforded a long-lived hole–electron pair, and photocatalytic water oxidation by the pentad was achieved in the presence of sacrificial oxidant.

My hat, it has three corners: Enantiopure C₃-symmetric triangular macrocycles were synthesized by means of triple asymmetric cyclopropanation. This method is successfully extended to the synthesis of an enantiopure hydrocarbon, which owes its chirality to asymmetric distribution of H/D atoms on the benzene rings.

Mighty Immobilized Peroxidase: The radical polymerization of methacrylate or vinyl monomers and cross-linkers was initiated by immobilized horseradish peroxidase (HRP) to prepare molecularly imprinted polymer (MIP) nanogels in aqueous media (see scheme). MIP nanoparticles with sizes between 50 and 300 nm were obtained with good binding properties and high selectivity for the target molecule, the herbicide 2,4-dichlorophenoxyacetic acid.

Azamacrocycles: A rhodium-catalyzed inner-sphere intramolecular C−H amination of tailormade acetophenone ketoximes tethered with either aryl or alkyl azides furnishes azamacrocyclic compounds with up to 36-membered rings. While substrates bearing aryl azides underwent a monomeric ring formation in high yields, a dimeric double cyclization took place exclusively with alkyl-azide-tethered ketoximes.

Know when to fold 'em: A linear molecular architecture equipped with complementary three-fold hydrogen bonding units embedded with a photoswitchable trans-tetrafluoroazobenzene moiety was synthesized. The trans to cis photoisomerism of the azobenzene unit induced changes in the molecular architecture as a result of intramolecular hydrogen bonding as evidenced by NMR spectroscopy and size exclusion chromatography.

No oxygen, no coupling: Molecular oxygen was shown to be crucial for the fast palladium-catalyzed cross-coupling of organolithium reagents developed herein. Reactions times down to 5 s provide a novel procedure for the preparation of radiolabeled compounds.

Multistage electron donor: The first hexakis(guanidino)benzene derivative donates four electrons at a record low potential.

Positive intermediates: The combination of non-terminal 1,5-diynes with cationic gold complexes enables the generation of highly reactive vinyl cations that can be used for the synthesis of unsymmetrically substituted dibenzopentalenes. Quantum-chemical calculations indicate a fast valence tautomer equilibrium between a gold alkyne complex and the vinyl cation.

Metal location: Both EPR and solid-state NMR spectra change on the substitution of Mg²⁺ by Mn²⁺ in two different ATP:Mg²⁺ fueled protein engines. While EPR spectra report metal binding and metal-center geometry, NMR paramagnetic relaxation enhancements localize residues at the binding site. Both techniques indicate the location of paramagnetic ions in proteins.

Carbon-rich compounds: An all-carbon double [7]helicene has been synthesized by regioselective cyclodehydrogenation. The compound represents the highest homolog of the double carbohelicenes. The twisted conformers D7H-1 and D7H-2 were separated by recrystallization, and their double helicene structures were elucidated by X-ray crystallography.

It takes only five consecutive steps from unsubstituted chrysene to obtain an all-kata-annulated arene tetracarboxylate, in which two heptahelicene segments are joined together. The bishelicene is formed in the achiral meso configuration, with the two helices having opposite pitches.

Pairs of peri MeO groups as mediators allowed seemingly distant Br or I substituents to exert regio- and diastereocontrol during naphthalene functionalization by electrophilic aromatic substitution. A bromonaphthalene-fused pyrano-γ-lactone resulted, which was dimerized in a Suzuki coupling. Removal of the methoxy groups and oxidation gave isomerically pure (+)-γ-actinorhodin in eleven steps.

The weakest link: Hydrosilanes activated by B(C₆F₅)₃ are known to cleave ethers as well as silyl ethers. However, more reactive tosylates are cleaved prior to those ethers, which allows for the chemoselective deoxygenation of diols and polyols. Other functional groups such as carboxyl groups are also tolerated. Defunctionalization of phenethyl tosylate motifs proceeds with anchimeric assistance (rearrangement).