The amine has landed! By employing the rhodium catalyst [Rh₂(esp)₂] in the presence of a readily available amine source (DPH), unactivated and styrene-type olefins can now be stereospecifally transformed, in high yields at room temperature, into valuable NH aziridine products. esp=α,α,α′,α′-tetramethyl-1,3-benzenedipropionic acid.

Yes they can! The groups of Zhu and Ma recently reinvestigated the synthetic route to aspidophilline A. These approaches are discussed in the context of the first total synthesis of the title alkaloid that was reported by Garg and co-workers in 2011.

New perspectives through enzymes: Recent breakthroughs have been achieved in the selective hydroxy functionalization of non-activated CH and CC bonds. Enzymes turned out to be suitable catalysts for the ω-hydroxylation of (substituted) alkanes and regioselective hydroxylation of aromatic hydrocarbons with atmospheric oxygen as the oxidant, and the asymmetric addition of water to non-activated alkenes.

One of the first oncogenes to be discovered and one of the most prevalently mutated tumor genes is Ras. Shokat et al. and Gray et al. have succeeded in discovering allosteric inhibitors and inhibitory nucleotide analogues, respectively, of K-Ras proteins (see scheme) that covalently and selectively bind G12C-mutant K-Ras. These strategies of specifically targeting a mutant form of Ras may offer an opportunity for cancer–selective therapies that spare normal tissue.

Near…︁far…︁wherever you are! Two chiral residues at the N-terminus of a helical foldamer are sufficient to induce a significant helical screw-sense preference. The capacity of this helix to transmit stereochemical information is exemplified by highly stereoselective transformations conducted over nanometer distances.

Weak yet influential: Fluorocarbons, the least coordinating of all halocarbons, establish secondary coordinative interactions with f elements. These interactions affect the stereochemistry of the complexes and provide examples of coordination polyhedra along distortion paths not seen before (see graphic).

GliTzy biosynthesis! A detailed picture of the key transformations during the biogenesis of gliotoxin has recently been created. Almost every intermediate in the biosynthetic pathway and the pertinent enzymatic machinery was isolated and fully characterized, thus placing the unique incorporation of the sulfur atoms as well as the formation of the epidithio bridge catalyzed by the key enzyme GliT and its consequences into the limelight.

All that′s nano is not gold: Definite, crystalline molecular compounds of noble metals have been known for gold for the last few years. Now a simple synthesis of a nanoscale silver cluster compound containing [Ag₄₄(S-C₆H₄COOH)₃₀]⁴⁻ ions has been found leading to gram scales quantities. Synthetic, structural, and bonding aspects of this novel compound are discussed in the context of metalloid clusters in general.

Unknown before 2013, a novel methodology utilizes CO₂ as a carbon source for the methylation of amines, with water as the by-product. This strategy offers a sustainable route to methylamines by converting CO₂ to value-added chemicals, using molecular hydrogen as a cheap and renewable reductant. The method may open novel applications for recycling CO₂ to bulk and fine chemicals.

Energetic MOFs with 1D, 2D, or 3D structures were synthesized through a self-assembly strategy by using energetic organic linkers to bridge non-toxic metal ions. This new concept for energetic MOFs opens opportunities for developing new-generation primary explosives in the field of energetic materials.

Glowing results with less phosphorus: Tremendous progress has been made recently in asymmetric intermolecular Heck chemistry. Previously unprecedented enantioselective Heck–Matsuda reactions have been accomplished, and mixed phosphine/phosphine oxides have been shown to be superior ligands in enantioselective Mizoroki–Heck reactions. All of this was achieved with chiral ligands containing few or even no phosphorus donors (see scheme).

No other cancer therapy target class caused more excitement than the programmed death-1 (PD-1) pathway related. Antibodies against PD-1 and PD-1 ligands represent a therapeutic breakthrough and are the first examples of broadly efficacious and durable cancer immunotherapies. Cancer for the first time seems to have transformed from an often incurable to a “clinically manageable” disease.

Adding value: The catalytic hydroamination of alkenes with amines holds promise to rapidly deliver value-added chiral amines from simple and accessible starting materials. The use of mild, Cu-catalyzed electrophilic amination strategies for the regioselective preparation of both linear and chiral branched amines is highlighted.

Esters—what else! A new strategy in NHC organocatalysis allows the α-, β- and γ-activation of saturated and unsaturated esters. The resulting acyl azolium intermediates efficiently participate in domino reactions with suitable substrates to generate synthetically valuable carbo- and heterocycles with very good diastereo- and excellent enantioselectivities.

Methods that interrogate different, yet overlapping structural-size ranges were integrated to gain high-resolution information on the Pyrococcus furiosus box C/D ribonucleoprotein complex. The new structure shows how 2′-O-methylation of RNA substrates through four active methyltransferases occurs in a strictly sequential manner.

A means to trifluoromethylate: The beneficial properties imparted by the trifluoromethylation of aromatic compounds continue to drive the discovery of novel reagents and reactions for the late-stage introduction of such moieties. Highlighted here is the recently discovered Sandmeyer trifluoromethylation approach, which now permits aromatic amines to be substrates in a direct trifluoromethylation strategy.

All in one: Perovskites are currently undergoing a renaissance as “allrounder” materials for solar cells. For a special type of methylammonium lead halide perovskites, a unique combination of properties, including high charge-carrier mobilities, exciton lifetimes, and panchromatic absorption, was observed, which renders this class of hybrid perovskites one of the most promising absorber and ambipolar charge-transport materials for all-solid-state solar cells.

Precisely tuning the active site by protein engineering has led to the development of a highly efficient Kemp eliminase (see structure with substrate in the binding pocket). The starting protein scaffold with only low activity originated from computational design, as no natural enzyme with this activity was known. This is a breakthrough in protein design, as novel catalytic activities are now in reach that match those of natural enzymes.

Hexacyclic framework: The total synthesis of the complex C₁₈-norditerpenoid alkaloid neofinaconitine has been achieved by a convergent approach. This remarkable synthesis featured two Diels–Alder cycloadditions and subsequent Mannich-type N-acyliminium and radical cyclizations to establish the unique hexacyclic core structure of the target molecule.

Release on demand: The pH gradients between extra- and intracellular regions can be utilized for the controlled release of drugs and biological cargos from delivery systems. Biocompatible carrier systems with pH-cleavable units must fulfill many other criteria as well, for example, a long blood circulation time. This can be achieved by tailored micro- and nanocarriers based on macromolecular architectures or stable self-assembled systems.