Reaction mechanisms articles from across Nature Portfolio

NMR spectroscopy is a powerful tool for studying chemical reactions, but short-lived intermediates are hard to capture. The authors present a system combining LED and rapid-injection NMR for in situ monitoring of photochemical processes, advancing the study of reactive species and kinetics.

Real-time single-molecule observation provides insights into transient intermediates that are normally inaccessible using ensemble measurements. This Review discusses the use of nanopores as both single-molecule nanoreactors and single-molecule sensors for elucidating reaction pathways and kinetics, while highlighting their potential to control covalent reactions under confinement.

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.

Experiments under upper-tropospheric conditions map the chemical formation of isoprene oxygenated organic molecules (important molecules for new particle formation) and reveal that relative radical ratios control their composition

Hydroxyl groups are among the most abundant functional groups, and thus, the development of efficient reactions for their conversion has significant importance in medicinal and process chemistry. Here, we present a redox-neutral Giese reaction via anodic oxidation to generate phosphonium ions in combination with a cathodic reduction to yield low-valent Fe-catalysts.

Non-covalent interactions between organocatalyst molecules can change catalytic behaviour, leading to changes in reaction rates and selectivities. This Review discusses how to identify such interactions, measure their effect on catalysis and ultimately how to avoid or exploit them in synthesis.

Amines are highly valued molecules, used to understand biological processes and in the discovery of new medicines. However, medium-sized cyclic and macrocyclic amines are extremely challenging to synthesize and are therefore underutilized. Now, up to 15-membered cyclic amines can be formed directly from smaller, more accessible rings via an organoborane-catalysed two-carbon-unit C–C bond insertion.

Despite the presence of para-cyclophanes in bioactive molecules, the synthesis of highly strained para-cyclophanes remains challenging. Now, a series of para-cyclophanes bearing highly distorted 1,4-disubstituted benzene subunits have been prepared from cyclic tertiary amines and aryne intermediates through an N-arylation and ring-expansion [5,5]-sigmatropic rearrangement process.

Gold redox catalysis has remained challenging owing to the high redox potential of the Au(I)/Au(III) couple (E° = 1.41 V). Now this challenge has been resolved by employing bidentate N-ligands with Au(I) catalysts in combination with hydrogen peroxide as a green and cost-effective oxidant.

Nature Computational Science is calling all researchers who develop and use generative models for molecular design and discovery to publish with us.

Electrochemical engineering offers a route to renewably powered CO₂ capture. Now, fluorescence spectroscopy diagnostics provides a means to probe the fundamental mechanisms within these otherwise opaque systems.

Sulfur(vi) fluoride exchange and modular diazotransfer reactions have advanced click chemistry, but their mechanisms and reactivity profiles are not well understood. Now, a computational study of these reactions provides mechanistic insights and predictive reactivity models for modular diazotransfer, facilitating the development of an easy-to-prepare and -handle diazotransfer reagent with excellent reactivity.