A highly regioselective hydroalkenylation of imines or aldehydes with styrene derivatives was realized by dual catalysis with Ni(cod)₂/PCy₃ and either TsNH₂ or PhB(OH)₂. This process provides an atom-, step-, and redox-economic pathway towards synthetically useful allylic amines and alcohols, and opens up a new avenue for the design of more versatile coupling reactions.

Superpower: The electrochemical coupling of an aluminum anode with a graphene cathode holds extraordinary promise in delivering the much sought after utility demands of ultrahigh power density, ultralong durability, enhanced safety, and flexibility. This Minireview deals with the accomplishments and challenges of Al–graphene batteries.

In the medium term: Effects of the reaction medium can be used to alter the reactivity and selectivity in synthetically useful procedures for the functionalization of aliphatic C−H bonds. This Review discusses the mechanistic features in terms of hydrogen bonding and acid–base interactions and shows that these effects can promote aliphatic C−H bond (de)activation toward hydrogen atom transfer reagents.

Sugar synthesis in solution: An automated system is designed for oligosaccharide synthesis. The automated process is based on enzymatic glycosylation and the use of a thermosensitive polymer and a commercially available peptide synthesizer.

The origin of reduced stability: The reason why ion–solvent complexes promote electrolyte decomposition on alkali/alkaline earth metal anodes is probed. The complexed cations can regulate the contribution ratio of carbon atomic orbitals in LUMOs of ion–ester complexes or totally change the atomic contribution in LUMOs of ion–ether complexes to reduce the energy level of the LUMO.

Organoboron compounds are versatile synthetic building blocks. A new strategy, namely a photochemical gold-catalyzed chemoselective Hiyama arylation of B,Si bimetallic reagents with diazonium salts, which is orthogonal to common strategies and therefore a unique tool for synthesis of valuable biarylboronates, has been developed. With this new methodology a wide array of diversely functionalized sp²- and sp³-hybridized biarylboronates were obtained.

Breaking down barriers: A computational study of the mechanisms of reactions of HNO with ferric heme proteins revealed that the HNO-binding process is rate-limiting, and reductive nitrosylation occurs by barrierless proton-coupled electron transfer, which provides the major thermodynamic driving force (see scheme). The origin of the difference in reactivity between metmyoglobin and catalase was also uncovered.

To understand the mechanisms of enol formation and stabilization over catalytically active metal surfaces, a mechanistic study was performed on keto–enol tautomerization of a monocarbonyl compound, acetophenone, over Pt(111) surface.

One, two, three: A triple bioorthogonal labelling strategy was developed to study the incorporation of three distinct monolignol reporters in lignin within plant cell walls. Alkynylfucose was also used in conjunction with monolignol reporters to show that non-cellulosic polysaccharide and lignin deposition can occur contemporaneously in the same cell wall. CuAAC: copper-catalysed alkyne–azide cycloaddition, SPAAC: strain-promoted azide–alkyne cycloaddition, DAR_inv: Diels–Alder reaction with inverse electronic demand.

Loaded: The majority of harmful atmospheric CO and NO_x emissions are from vehicle exhausts. Both CO and NO_x emissions can be simultaneously removed under realistic exhaust flow, using highly loaded (2 wt %) atomically dispersed palladium in the extra-framework positions of a small-pore chabazite zeolite material. To do this, a simple and scalable route to highly loaded Pd and Pt small-pore siliceous zeolites is developed.

Peptides and polymers: Polymer/cyclic peptide conjugates form supramolecular tubisome structures with a hydrophobic core and a hydrophilic shell. They perforate the lysosomal membrane in cells to release a small molecule into the cytosol.

Li⁺ conductor: An anionic aluminum based metal–organic framework (MOF) was synthesized which exhibits the highest Li⁺ loading reported to date (2.50 wt %) and an ionic conductivity of 5.7×10⁻⁵ S cm⁻¹.

Fast, enrichable photocrosslinking: Photocrosslinking reagents with methanethiosulfonate and diazirine functionalities have been developed. After crosslinking and reduction, a thiol tag stays at the interaction site, to be located by mass spectrometry and used for enrichment of even low abundance crosslinks. A UV LED irradiation platform reduces crosslinking times to 10 s.

An autonomous swelling-deswelling oscillation of polymer gels was achieved in a hydrated protic ionic liquid (PIL) as a proton source for the Belousov–Zhabotinsky (BZ) reaction. The PIL acts as a medium for the BZ reaction and is a promising material for developing self-oscillating gels under milder conditions.

A step up: Vertical step-growth polymerization of a monomer A-B through individual A–A and B–B coupling reactions driven by electrochemically positive and negative bias on a self-assembled A or B electrode enabled the sequence- and topology-controlled synthesis of molecular wires with single-molecule precision (see picture). The resulting surface-confined molecular wires showed fast electron transfer and excellent electrocatalytic performance.

V for victory: A two-dimensional MoN-VN heterostructure is investigated as a model sulfur host. The heterostructure can regulate polysulfides and improve sulfur utilization efficiency, resulting in superior rating and cycling performance. More importantly, incorporation of V in the heterostructure can effectively tailor the electronic structure of MoN, leading to enhanced polysulfides adsorption.

Lighting the way: Inspired by the light-driven proton pump bacteriorhodopsin, an artificial light-powered molecular motor was developed by functionalizing synthetic nanochannels with azobenzene derivatives. These nano-confined machines exhibit autonomous selective transport behavior over long distances upon simultaneous irradiation with UV (365 nm) and visible light (430 nm).

Myths and realities: The archetypal “carbocatalytic” conversion of benzyl alcohol into benzaldehyde was critically studied. Rather than acting as a “carbocatalyst”, graphene oxide (GO) is reduced and a major side product, dibenzyl ether, is also formed. In this transformation, GO underwent extensive loss of oxygen and can be thus reclassified as a reagent.

Digital inorganic chemistry: 3D printing enables fabrication of digitally defined and structured hydrothermal reactors which can be used for multistep hydrothermal synthesis. This “reactionware” approach increases the parameter space and kinetic control during a hydrothermal process, allowing preparation of a series of polyoxometalate (POM) containing metal–organic frameworks (MOFs) unavailable by “one-pot” methods.

Predicting selectivity: Decarbonylative borylation of carboxylic acids is reported. By circumventing the challenging decarboxylation, this strategy provides a general synthetic platform to access arylpalladium species for a wide array of bond formations from abundant carboxylic acids. Computations illustrate the origin of activation selectivity.

One, two, lactam! A domino synthesis of unsaturated γ-lactams is reported to proceed by a palladium-catalyzed amination of allylic alcohols. An intramolecular carboxyl group acts as a stereodirecting functional group, enabling the formation of Z-configured γ-amino acids and subsequent cyclization to the targeted lactam scaffolds. This procedure is atom-efficient and mild, and highlights a new way of allylic alcohol activation under ambient conditions.

Li−S batteries: A lithium-compatible and strongly polysulfide-solvating high-dielectric electrolyte based on tetramethylurea was proposed to direct a solvation-mediated radical reaction pathway. It enables Li−S pouch cells to deliver an energy density of 324 Wh kg⁻¹. Key: red=electrochemical, black=chemical, dashed=diffusion/precipitation.

Character building: Derivatives of two diazuleno-s-indacene isomers were synthesized, and they show different diradical character depending on the fusion mode and substituents. They maintain the aromatic character of azulene and anti-aromatic feature of the s-indacene. Upon oxidation to the dication, two aromatic tropylium rings are formed, resulting in a shift of the local (anti)aromaticity.

More colors for MRI: Perfluorocarbon-encapsulated silica nanoparticles, PFCE@SiO₂, TPFBME@SiO₂, and PFTBA@SiO₂, that exhibit ¹⁹F NMR peaks with different chemical shifts were developed. These nanoprobes showed ¹⁹F MRI multiplexed signals in MR imaging of phantoms. Finally, ¹⁹F MR imaging with triple colors was achieved in a living mouse.

Building on CO: A primary bis(phosphido) complex gives both hydrogen atoms from each phosphorus center to a single carbon atom when treated with carbon monoxide. This is a rare example of the conversion of CO into a formyl-like species through intramolecular proton transfer.

COF chirality: A general and efficient strategy has been developed to introduce chirality into covalent organic frameworks (COFs) by covalently immobilizing biomolecules into achiral COFs. The biomolecules⊂COFs can serve as chiral stationary phases for efficient chiral separation of a broad range of racemates.

The key amination step of the ketone precursors in a biocatalytic synthesis of substituted pyrazines and pyrroles is mediated using a transaminase (ATA). Treatment of α-diketones with ATA-113 in the presence of an amine donor yielded α-amino ketones which underwent oxidative dimerization to the pyrazines. Selective amination of α-diketones in the presence of β-keto esters afforded substituted pyrroles in a biocatalytic equivalent of the classical Knorr pyrrole synthesis.

Highly selective: A hybrid photosensitive ferroelectric based on (diisobutylammonium)₃ClCoCl₄ shows spectrally customized photosensitivity with distinct photocurrent generation under specific wave-band illumination.

Dimers are forever: Two crystallographic studies of the dimer of 8-electron superatom clusters: [Au₂Ag₄₂(SAdm)₂₇]⁺ and [Au₂Ag₄₈(S-tBu)₂₀(Dppm)₆Br₁₁]³⁺ enrich the understanding of metal superatom molecular clusters and suggest the possibility for further assembling metal superatom building blocks into higher order superatom molecules.

Particles in motion: Janus liquid droplets can be used as building blocks in an active propulsion system. Using an ionic liquid, the droplet system can be tuned from core–shell to Janus and multipatches by using surfactant-based methods. The approach was stimulated by the success of electrohydrodynamic flow produced by an alternating electric field to produce motion of colloidal particles; its usefulness to also propel ionic liquid droplets is demonstrated.

Diffusion of the invisible state: A CPMG NMR spectroscopy experiment allows measurement of translational diffusion constants of protein excited states. The experiment exploits methyl ¹H 3Q coherences and applies encode/decode gradients flanking a CPMG element so that heretofore unmeasurable hydrodynamic properties of invisible states can be obtained.

TaN was used in a photocatalytic reaction because of its own optical properties. It is shown that the improved electron-hole separation and transfer over asymmetrical TaN can account for its activity enhancement with visible-light irradiation.

Deep sequencing was applied in a new concept of library preparation for detection of RNA modifications. Modified RNA is treated by alkaline hydrolysis, dephosphorylated, and subjected to aniline cleavage of abasic sites. The resulting 5′-phosphates in RNA are used for specific ligation of the sequencing adapter. The method can be applied for specific and sensitive detection of m⁷G, m³C, and (D) residues in RNAs.

An enantioselective nanomaterial has been constructed. In the oxidation of chiral DOPA, the nanozyme with d/l-Cys shows preference to l/d-DOPA, respectively. Calculation of apparent steady-state kinetic parameters and activation energies together with molecular dynamics (MD) simulations showed that the different affinity precipitated by hydrogen bond formation between chiral Cys and DOPA is the origin of the chiral selectivity.

Assembling lanthanide–transition-metal (4f–3d) clusters Ln₅₂Ni₅₆ (Ln=Eu, Pr, Nd and Gd) onto CdS composites achieved enhanced photocatalytic H₂ production. Some Ni²⁺ ions in the clusters were exchanged by Cd²⁺ to form Ln₅₂Ni_56−xCd_x/CdS composites. An Eu₅₂Ni_56−xCd_x/CdS species shows the highest activity of 25 353 μmol h⁻¹ g⁻¹ and an apparent quantum efficiency of 42.4 %.

K⁺ sensing: A light-addressable electrochemical K⁺ sensor is introduced that consists of a thin polymer film containing an ionophore deposited on a semiconducting silicon electrode. Ferrocene is covalently attached to oxide-free silicon and the electrode exhibits surface confined electrochemistry under light illumination. The sensor exhibits a Nernstian response to [K⁺] in a light-defined spatial region. Changes in extracellular [K⁺] associated with living cells upon stimulation are monitored electrochemically.

True blue: By utilizing BN/CC isosterism and topochemistry, visible-light-induced photodimerization of vinylpridine-appended tetraarylaminoborane (TAAB) was accomplished within a record low reaction time of 1 h without the need for a photoredox catalyst or template. Both the monomer and photodimer exhibit distinctive photophysical properties with deep-blue delayed fluorescence (DF) features in solution and in the solid state.

Doctor node: Photocatalytic conversion of diluted CO₂ with high efficiency and selectivity can be achieved on Ni metal–organic framework (MOF) monolayers (Ni MOLs). The initial adsorption of CO₂ molecules is the critical step and depends on the nature of the metal node.

A fine pair of tweezers: A di-gold(I) metallotweezer shows three different coordination modes depending on whether it is bound to Cu⁺, Tl⁺, or Ag⁺.

Color tuning: Crystals of the fluorene derivative BrFlu−CBr exhibit fluorescence-phosphorescence dual-emission upon introduction of a mechanical stimulus, without excitation by a UV lamp. Upon extended exposure to the mechanical stimulus, the triboluminescence emission changes from cyan to blue. After removal of the mechanical stimulus, green-white phosphorescence is observed.

Completely different sintering behaviors of gold nanoparticles on distinct anatase TiO₂ surfaces are unveiled by in situ TEM. OR=Ostwald ripening, PMC=particle migration and coalescence.

I to B: A metal and additive-free radical borylation using a commercial diboron reagent is introduced. Alkyl and aryl iodides are borylated under very mild conditions in good to excellent yields.

Radicals and Co: An enantioselective radical process has been established using cobalt(II)-based metalloradical catalysis (MRC) for stereoselective amination of aliphatic C−H bonds at room temperature to form chiral 1,3-diamines under neutral and non-oxidative conditions. The cobalt(II)-catalyzed C−H amination features an unusual degree of functional-group tolerance and chemoselectivity.

Co catalyst as co-catalyst: A Pd^II-catalyzed oxidative carbocyclization of the rational designed enallenynes using molecular oxygen is reported. By applying a bifunctional catalyst (Co(salophen)-HQ) as an efficient electron transfer mediator, enallenynes are effectively arylated to the corresponding six-membered carbocycles in good yields.

A one-pot, transition-metal-free, domino Michael/S_NAr process was devised for the regioselective synthesis of polyfunctional naphthalenes by employing nitromethane and ortho-haloaryl ynones. Nitromethane was utilized as a one-carbon carbanion source that is incorporated into a variety of ynones, ending up as an aromatic nitro substituent. This reaction was used in the total synthesis of the polycyclic alkaloid macarpine.

The ketenimine species generated in situ from sulfonyl azides and terminal alkynes were trapped by the chiral guanidine/Cu^I complex and followed by a [2+2] reaction, which afforded various spiro-azetidinimine oxindoles in good yields and excellent stereoselectivities. Control experiments and X-ray crystallography were used to probe into the interaction of the chiral guanidinium salt with the copper salt.

A mild and general, nickel-catalyzed Mizoroki–Heck reaction of unactivated alkyl bromides is described. The reaction proceeds efficiently using a wide range of primary and secondary alkyl bromides, and examples of intermolecular cross-couplings are provided. Alkene regioselectivity is significantly enhanced over prior carbocyclizations using palladium catalysis, and mechanistic investigations are consistent with a direct carbocyclization.

A mild three-component system was developed for the preparation of alkylboronic esters by ring-opening 1,3-hydroborations of non-activated cyclopropanes. This method has good functional group compatibility and can serve as a powerful synthetic tool for late-stage borylative ring-opening of cyclopropanes in complex compounds.

Controlling confusion: Incorporation of α,β′-pyridine into a [26]hexaphyrin (1.1.0.1.1.0) frame afforded 29,33-diaza-A,D-di-p-benzi[26]hexaphyrin, which was shown to have a 26-electron π-delocalized structure. A stepwise protonation of pyridine moieties resulted in N-confused or doubly N-confused conformers of the original macrocyclic frame.

A palladium-catalyzed decarbonylative cross-coupling reaction of acid chlorides with a difluoromethyl zinc reagent allows access to difluoromethylated compounds. The transformation proceeds at room temperature and shows broad functional group tolerance, thus providing a general and efficient method for decarbonylative difluoromethylation of a wide range of aromatic carboxylic acids.

Putting a number on it: An equation is derived based on Pauling's equation and is shown to accurately estimate the bond enthalpies of small molecular fragments to transition-metal surfaces.

Zn₁₀In₁₆S₃₄ atomically thin nanosheet arrays were synthesized and their photoelectrochemical water splitting activities studied. Performance enhancement was attributed to the fast photoexcited electron–hole pair separation, decreased surface transfer impedance, prolonged carrier lifetime, and reduced overpotential of the oxygen evolution reaction.

Admirable self-control: A self-switchable route to multiblock copolymers from three-component feedstocks (see picture) was developed with commercially accessible organocatalysts. The one-step procedure showed perfect chemoselectivity, living nature, and applicability to a wide range of monomers.

Mixtures of three commercial monomers, produced and used at large scale in existing polymer manufacturing, were applied in a switchable catalytic process to deliver new multi-block polyesters. The aluminium catalyst delivers polymers of 3, 7, 11, 15, 19, 23, and 27 block units with outstanding selectivity.

N-doped graphene-like layered carbon (NG) could be synthesized by a metal-free pyrolysis route from glucose, fructose, and 5-HMF, which are widely available biomass or biomass derivatives. A well-developed thin-layer structure with large lateral dimensions could be observed for 5-HMF-derived NG, which could be used as a metal-free catalyst in alkene epoxidation.

Te time: The first direct catalytic method for the formation of C(sp²)−TeCF₃ bonds has been developed. It relies on a Pd/Xantphos catalytic system and allows for the trifluoromethylellurolation of aryl iodides. Computational and experimental mechanistic analyses shed light on the privileged activity of Xantphos in this transformation.