Review Articles

Thianthrene, long used in materials science, has recently emerged as a powerful reagent in organic synthesis. Its unique electronic structure enables access to diverse aryl, alkenyl and alkyl thianthrenium salts, which exhibit reactivity beyond conventional (pseudo)halides. This Review highlights the fundamental properties, distinctive reactivity and synthetic applications of these thianthrenium salts.

Three-component, iron-based catalytic transformations offer a promising and sustainable approach to building complex molecules in a single step. This Review highlights advances and ongoing challenges in the development of iron-catalysed difunctionalization of alkenes. Mechanistic insights that enhance our understanding and guide the development of new transformations are discussed.

One-carbon compounds, including carbon dioxide and methane, represent a sustainable resource for chemical conversions. This Review highlights recent advances in the biochemical upgrading of one-carbon substrates to value-added products using a combination of cellular, cell-free and abiotic catalysis strategies.

Synthetic molecular systems exhibiting allosteric regulation are used in purification, sensing, delivery and catalysis. Metal–organic cages provide a versatile platform for allosteric regulation due to their structural diversity and tunable cavities. This Review discusses recent advances in allosteric regulation with metal–organic cages, emphasizing design principles, applications and future challenges.

Although π-bonds are typically associated with having well-defined arrangements of atoms, ring constraints can lead to geometric distortion, resulting in heightened reactivity. These effects can be leveraged to enable synthetic transformations. This Review features processes wherein geometric distortion is leveraged to provide rapid access to structurally complex products.

CO₂ hydrogenation is promising for the conversion of waste CO₂ emissions into value-added chemicals. This Review examines the atomic-level design of heterogeneous catalysts with precise active sites and related catalytic reaction engineering for tuning CO₂ hydrogenation selectivity.

Well-defined vinyl polymers with ultrahigh molecular weights are promising for use as high-performance materials and are now made increasingly accessible by photocontrolled radical polymerizations. This Review discusses the methods developed for the synthesis of such polymers and their potential applications.

The emergence of high-entropy materials affords opportunities to harmonize precision and disorder for materials design. This Review highlights the synthesis principles and strategies towards controllable and predictive fabrication of high-entropy materials with complex chemical compositions, engineered microstructures and tailored atomic configurations.

Digital workflow representations in automated and autonomous chemistry laboratories can achieve transferability by using abstract concepts. However, such abstractions must abide by certain rules to ensure reproducibility. Lessons learned from computer science for responsible abstraction are translated into an automated chemistry laboratory context to guide digital workflow development towards reproducibility.

M_nL_2n cages are versatile supramolecular architectures and have become increasingly synthetically accessible. This Review examines the multiple roles that can be filled by M_nL_2n cages in catalysed chemical reactions.

Cell-based polymerization offers a promising avenue for integrating synthetic chemistry with biological systems. By leveraging cellular machinery, native chemical environments and external stimuli, the in situ-synthesized polymers hold the potential to impact diverse biomedical research domains, from the regulation of cell behaviour to targeted therapeutics.

Carbon-based fuels and value-added chemicals can be produced sustainably using electrochemical CO₂ reduction (CO₂R). This Review examines the expansion of scope through the coupling of CO₂R with heteroatomic co-reactants.

Geometry control in organic reactions can be used to promote dynamic processes or stabilize reactive transition states. This Review discusses the concept of geometry control, its impact on transition states and bonding, as well as the reactivity and properties that emerge as a consequence of constraining molecules.

Synthesis of fuels and chemicals from renewable biomass is an important way to achieve sustainable development. This Review summarizes catalyst design for steering interfacial charge transfer and radical intermediate reactions in photocatalytic biorefineries.

The discovery of immunosuppressive natural products and synthetic strategies to make these compounds have impacted biology and ultimately human health. This Review highlights synthetic examples of such compounds, which have the potential to discover immunological mechanisms.

Traditionally, enzymes were not commonly used as catalysts by organic and pharmaceutical chemists owing to insufficient stereoselectivity. However, this changed with the onset of directed evolution. This Review introduces mutagenesis methods, describes the enzyme-catalysed production of specific pharmaceuticals and presents further examples.

Enantioselective synthesis of medium-sized rings by organocatalytic cycloadditions offers opportunities that are complementary to metal-catalysed cycloadditions. This Review discusses the ability of organocatalytic cycloadditions to synthesize stereodefined medium-sized ring architectures, critically evaluates current synthetic strategies, and highlights avenues for further development.

Catalytic enantioselective synthesis of all-carbon quaternary stereocentres is a long-term challenge in organic synthesis because of substantial steric repulsion and dissimilarities between the substituents around the stereocentre. This Review presents how the desymmetrization strategy plays an important role in constructing these types of motifs.

Performing enantioselective photocatalytic reactions with visible light is a challenging task that has seen substantial advances with the development of new catalysts. Although many approaches utilize dual-catalytic systems in which the photocatalyst is separate from the chirality-inducing moiety, in this Review bifunctional photocatalysts that perform both roles are discussed.

The electrocatalytic oxygen evolution reaction (OER) balances the hydrogen evolution reaction when splitting water into hydrogen and oxygen. This review highlights the need for new theory, electrochemistry and operando spectroscopy to enable knowledge-driven synthesis of new OER electrocatalysts.