Reviews & Analysis

Three unprecedented selective bioconjugation methods for serine, methionine and lysine have been realized. Specifically, chemoselectivity for serine, site-selectivity for methionine and site-specificity for lysine were achieved.

Transient directing groups enable selective metal-catalysed C–H functionalization reactions to give diverse products. These directing groups form and dissociate in situ, such that their use is an efficient route to complex organics, examples of which are summarized in this Review.

Lipid membranes were likely critical in the transition from matter to life and are key to the bottom-up development of artificial cells. This Review highlights prebiotic, synthetic and biochemical strategies to construct lipid membranes that facilitate life-like cellular functions.

Although a stalwart in materials science, electron diffraction has only recently become popular for characterizing molecular structures. This Perspective describes practical aspects of the method, which affords complementary information to X-ray and neutron diffraction.

Late-stage C–H functionalization of complex molecules has emerged as a powerful tool in drug discovery. This Review classifies significant examples by reaction manifold and assesses the benefits and challenges of each approach. Avenues for future improvements of this fast-expanding field are proposed.

Enantioselective transition-metal-catalysed nitrene transfer is a powerful approach to access valuable amines. This Review describes recent catalyst designs for asymmetric aziridinations of C=C groups and aminations of C–H bonds.

What do a rock in a river, a red blood cell in our body and the electrodes inside a car battery have in common? Charged surfaces in contact with water. Although a unified approach to study such a variety of systems is not available yet, the current understanding — even with its limitations — paves the road to the development of new concepts and techniques.

This Review identifies competitive advantages and drawbacks of heterogeneous and homogeneous catalytic hydrogenation, as well as enzymatic catalysis, photocatalysis and electrocatalysis, for CO₂ reduction to methanol.

Recent findings on the skeletal rearrangement of polycyclic aromatics under oxidative and acidic conditions are envisioned to help development of these Scholl reactions into a more useful and versatile method for synthesizing polycyclic aromatics on the basis of rational design rather than luck.

State-of-the-art synthetic methods regularly encounter challenges associated with cost, safety and/or efficiency when proposed for large-scale applications. This Review highlights recent applications of novel reactions/technologies (e.g. photoredox, electrochemistry, C–H activation, reductive coupling and flow chemistry) on the process scale.

Radical philicity — the ability of a radical to act as a nucleophile or an electrophile — is an important, yet often poorly understood, concept. In this Review, we present a qualitative method to understand and predict radical philicity by classifying the typical reactivity of more than 30 types of radicals into nucleophilic or electrophilic behaviour.

Radical-pairing interactions were, until recently, considered something of a chemical curiosity. But these weak interactions, on par with hydrogen bonds, are easily switched on and off and, as a result, have become widely exploited in supramolecular chemistry, particularly in the assembly of out-of-equilibrium structures.

Molecular decoders are single host matrices able to differentiate analytes by their distinct structural accommodations. Ten years ago, Susumu Kitagawa and co-workers described the prototypical molecular decoder and paved the way for molecular sensing. We now revisit this seminal study and discuss some of the advances that have followed.

Implementing effective chemomechanical coupling in the microscopic world is challenging. This Perspective describes recent advances of chemically-powered swimming or diffusion of objects on the molecular scale, nanoscale and microscale.

Charge-separated organic molecules find diverse applications as functional materials. This Review describes zwitterionicity as a general design principle for ‘smart’ coordination chemistry and the activation of strong bonds.

The early 1980s witnessed the report of a molecular ruthenium complex active for dehydrogenation of alcohols and hydrogenation of carbonyl compounds. The ligand used represented a new paradigm that influences homogeneous catalysis to this day.

Finding the best approximation to the exact functional of electron density is the central challenge of density functional theory (DFT). In 2005, Zhao, Schultz and Truhlar paved the way to the development of approximate DFT functionals that can offer universally accurate treatment of different chemical systems and properties.

Dual-locked optical probes change their optical signals when they respond to two biomarkers of interest. This facilitates real-time imaging of multiple interrelated biomarkers in living systems and, thus, provides opportunities to better understand pathological events and enhanced diagnostic specificity.

Machine learning is starting to reshape our approaches to excited-state simulations by accelerating and improving or even completely bypassing traditional theoretical methods. It holds big promises for taking the optoelectronic materials design to a new level.

The recent COVID-19 pandemic and continued use of chemical weapons worldwide demonstrate the risks posed by biological and chemical threats. This Review highlights the importance of functionalized fabrics and surfaces to combat these threats and the progress made in their preparation.