Rewrite the textbooks! The stereospecific bimolecular substitution reaction (S_N2) is usually limited to primary and secondary electrophiles. The Shenvi group has developed a method in which tertiary alcohol substrates are converted into isocyanides with configurational inversion. Intriguingly, tertiary hydroxy groups react selectively in the presence of unprotected primary and secondary hydroxy groups.

More participants, yet efficient reactions: Multicomponent reactions (MCRs) have found application in polymer chemistry both in the synthesis of multifunctional monomers and in post-polymerization modification. Examples include the Passerini three-component reaction, the Ugi four-component reaction, and the copper-catalyzed MCR (see scheme).

New iron dinitrogen complexes are crucial to a catalytic ammonia synthesis in homogeneous solution and establish new structural motifs related to the iron–molybdenum cofactor of the enzyme nitrogenase (see scheme; BAr^F= B[3,5-(CF₃)₂C₆H₃]₄). These findings are put into the context of 50 years of synthetic nitrogen fixation and latest developments regarding the crystal structure and the molecular mechanism of nitrogenase.

Cyclopropenylidene carbenes have been found to be efficient catalysts for the intermolecular Stetter reaction between aromatic aldehydes and α,β-unsaturated ketones. In this transformation, the cyclopropenylidene proved superior to more traditional thiazolium- and triazolium-derived carbenes. Preparation and evaluation of a chiral analogue have also been reported.

Enantioselective wetting: Regulating the surface wettability of materials through chiral molecules provides new insight into the design of chiral materials. By taking advantage of a reversible conformational transition, smart polymers present an ideal platform for translating weak chiral signals into macroscopic properties of materials, thus resulting in a distinctive wettability switching driven by chirality (see scheme).

Let there be light, let it be white: Recent developments in the use of chromophore-based gels as scaffolds for the assembly of white-light-emitting soft materials have been significant. The main advantage of this approach lies in the facile accommodation of selected luminescent components within the gel. Excitation-energy-transfer processes between these components ultimately generate the desired light output.

Hit the mark: The development of a short synthesis of ingenol may mark the beginning of a new era of natural products synthesis, an era where structural complexity does not deter the development of processes amenable to scale up. This may foster the exploration of biologically relevant chemical space and pave the way to the development of commercial syntheses of natural products.

The X factor of tropospheric oxidation: Formaldehyde oxide, the smallest “Criegee intermediate”, has been observed spectroscopically in the gas phase. Field studies provide increasing evidence that Criegee intermediates play a key role in tropospheric oxidation (see scheme).

How are biomolecules transported between cellular compartments? James E. Rothman, Randy W. Schekman, and Thomas C. Südhof made seminal contributions to answering this question with their research into the molecular mechanism of intracellular vesicle transport. For their achievements, the researchers were awarded the Nobel Prize in Physiology or Medicine on October 7, 2013.

Green light for a new method: The protein UnaG shows bright green fluorescence in conjugation with bilirubin. The high affinity and specificity of UnaG allows for the fast and reliable measurement of bilirubin levels in human serum, which could improve the diagnosis of neonatal jaundice and other disorders based on insoluble bilirubin. UnaG expands the toolbox of fluorescent proteins with new features, such as oxygen independence and fast inducibility.

The significance of computer simulations in such varied fields as chemistry, biophysics, structural biology, and materials science is emphasized by the award of the Nobel Prize in Chemistry 2013 to three of the most important pioneers of computational chemistry. Computer simulations are widely used today to interpret experimental results, to test hypotheses, and as inspiration for experiments.

Radicals can do it! Oxidative coupling processes that proceed by a single-electron-transfer mechanism have been established. Recently developed methods demonstrate the ability of non-precious-metal catalysts to act as efficient catalysts for such transformations. This concept provides a sustainable approach for the construction of CC and CX bonds.

A victory in the pocket: An international team of chemists and biophysicists have resolved the long-standing question of the structure of the active site of the [FeFe] hydrogenases by assembling the active enzyme with a version of the active site synthesized in vitro (see scheme; HydF is a scaffold protein, HydA1 is a natural hydrogenase). The protein incorporating the diiron complex 2 showed similar activity to that of the natural enzyme.

On the right track: Recent advances in noncontact atomic force microscopy (nc-AFM) have enabled the bond-resolved imaging of reaction pathways. In particular, unprecedented insights into complex enediyne cyclization cascades on silver surfaces were gained by single-molecule imaging.

Not just any old iron ion: A linear, two-coordinate ionic Fe^I complex (see scheme) with a S=3/2 ground state has a large energy barrier for magnetization reversal, U_eff=226 cm⁻¹, and undergoes slow magnetic relaxation in the absence of an applied magnetic field. The preparation of complexes with these properties is a step towards the eventual practical application of single-molecule magnets.

Diastereodivergent is cool: The development of catalytic systems able to generate each and every one of the possible product diastereoisomers from the same starting materials (i.e., that are “diastereodivergent”) is an emerging field in asymmetric catalysis. The possibility of designing such systems in a rational manner based on dual catalysis has now become reality.

Golden times: Recent breakthroughs in gold-catalyzed transformations using nanosized homogeneous gold catalysts are highlighted. These catalysts have activities and stabilities comparable to (or even surpassing) heterogeneous catalysts. Well-defined, ligand-supported gold clusters turned out to be active in homogeneous catalysis, a catalyst concept which holds potential for future studies.

Antimatter: Once studied primarily for their antiaromatic properties, pentalenes are rapidly becoming important π-systems for novel electronic materials (see scheme). Recent developments in this area are summarized.

New members in the GPCR photo gallery! Crystal structures of class B G protein-coupled receptors, which bind peptide hormones, have been solved [see picture of the corticotropin-releasing factor receptor 1 (blue) and a bound allosteric nonpeptide antagonist (green)]. The structures provide a basis for a rational design of better drugs for diabetes, osteoporosis, migraine, or depression.

Death trap: The rational design of metal/N-heterocyclic carbene complexes allows mitochondria to be targeted. Activation of several apoptotic processes (which do not include direct DNA damage) induces cell death and significant tumor suppression.