Reaction mechanisms articles from across Nature Portfolio

Allylic substitution reactions have emerged as a powerful tool for the construction of C − C/X bonds. Here, the authors develop a migratory strategy of allylic arylation under the catalysis of nickel and lanthanide triflate.

Oxygen reduction reaction plays a key role in many applications of MoS₂-based materials. Here, using first-principles simulations, the authors find the enhanced oxygen-reduction activity with a biperiodic chemical trend on the lanthanide-doped MoS₂.

Polycyclic N-heterocycles are important structural motifs commonly found in bioactive compounds, however, their selective construction via the cyclization of allenynes remains challenging. Here, the authors develop a copper-catalyzed, temperature-controlled regioselective hetero Diels-Alder reaction of allenynes with cis diazenes to produce a diverse array of polycyclic N-heterocycles.

The versatility and importance of β,γ-unsaturated ketones has been appreciated for a long time in synthesis and medicinal chemistry. Here, the authors use carboxylic acids and readily available olefins as substrates for transformations involving N‑heterocyclic carbene catalysis, hydrogen atom transfer catalysis, and photoredox catalysis for the synthesis of β,γ-unsaturated ketones.

Electrocyclic reactions proceed through critical geometries, which are known as pericyclic transition states in thermal reactions and pericyclic minima in photochemical reactions. Here, the authors image the structure of a pericyclic minimum in real time using a combination of ultrafast electron diffraction and ab initio dynamics simulations.