Organocatalysis articles from across Nature Portfolio

While a variety of well-established methods enable the control of a stereogenic center, a catalytic method for controlling a stereogenic axis in one substrate is typically unavailable for controlling axial chirality in other substrates with a similar structure. Here, the authors report o-amidobiaryl as a flexible platform for chiral phosphoric acid catalyzed atroposelective dynamic kinetic resolution.

The catalytic asymmetric dearomatization (CADA) reaction is a powerful protocol for the assembly of three-dimensional cyclic compounds but phenols have been considered challenging substrates. Here, the authors report the chiral phosphoric acidcatalyzed divergent intermolecular CADA reactions of phenols with azoalkenes to obtain tetrahydroindolone and cyclohexadienone products in good yields with excellent ee values.

meta-Selective acylation of arenes typically requires directing groups or steric hindrance. Now, a combined N-heterocyclic carbene and organic photoredox catalysed of electron-rich arenes, using acyl imidazoles as acylating agents, is reported. Mechanistic studies reveal the process proceeds through single-electron oxidation and radical–radical coupling steps.

Metal-free versions of azide–alkyne cycloadditions could find widespread applications in biomedical contexts. Here, the authors report an assembly-driven, regioselective azide–alkyne cycloaddition.

Stabilization of RNAs for storage, transport and biological application remains a profound challenge. Now, it has been shown that reversible 2′-OH acylation with easily accessible acylimidazoles unlocks efficient protection of RNA. RNA can be deprotected by non-basic nucleophiles or spontaneously in cells to restore RNA functions.

Enantioenriched β-amino acid derivatives are attractive synthetic targets, considering the significance of these motifs in medicinal and material chemistry. Now, using ambiphilic ynamides as two-carbon synthons in a four-component reaction, three classes of β-amino amides with well-defined stereocentres can be accessed.

A strategy to synthesize well-defined main-chain fluoropolymers from gaseous fluoroalkenes under ambient conditions is developed. This general approach allows for the facile tailoring of the sequence and topology of fluoropolymers comprising various comonomers.

The direct carbon isotope exchange reaction on α-amino acids is highly desirable, as existing labelling methods require several synthetic steps and harsh conditions. Now, an aldehyde-catalysed carboxylate exchange with isotopically labelled *CO₂ has enabled the direct formation of ¹¹C, ¹³C and ¹⁴C-labelled α-amino acids.

Coordination of a photoswitchable chiral phosphate ligand to an achiral manganese(iii)-salen complex yields a catalyst that can produce either enantiomer of an epoxide from a single alkene substrate. This enantiodivergent catalysis is governed by the transfer of the chirality of the phosphate ligand to the manganese(iii)-salen complex.