Stereochemistry articles from across Nature Portfolio

The catalytic enantioselective synthesis of inherently chiral calix[4]arenes remains underexplored. Herein, the authors report the enantioselective synthesis of inherently chiral calix[4]arenes using a chiral phosphoric acid-catalyzed aminative desymmetrization method.

Catenanes can exhibit chirality even when their component rings are achiral. Here an isostructural desymmetrization strategy is developed, demonstrating that two achiral rings, each featuring two mirror planes and a two-fold axis of symmetry, can form a catenane with tuneable mechanical chirality.

Switchable skeletal editing is valuable in drug discovery, but controllable methods for chemodivergent modifications of azaarenes are challenging. Now transformations of quinolines have been achieved by leveraging cyclizative rearrangement strategies, enabling the construction of four different frameworks, including the enantioselective skeletal editing of quinolines into benzazepines.

Enantioenriched α-chiral β-fluorinated ketones are valuable structural motifs with application in several fields. Herein, the authors report a novel family of chiral thiazolium carbenes with broad steric and electronic tunability, allowing for the acyltrifluoromethylations of simple unactivated olefins in high enantioselectivity, yielding enantioenriched α-chiral βfluorinated ketones.

The ring opening of cyclopropenes provides a compelling platform for the rapid synthesis of various polysubstituted acyclic alkenes, but radical-mediated reactions of this type remain underexplored. Here, the authors report an aminative ring-opening of cyclopropenes with iron-aminyl radical to afford tetrasubstituted alkenyl nitriles.

The introduction of chiral sulfur(VI) into polyaromatic hydrocarbons has been a formidable challenge due to the intricate enantioselective discrimination and embedded linkages with the heteroatoms in the polyaromatic systems. Herein, the authors report an enantioselective palladium-catalyzed desymmetrization of diaryl sulfoximines and sulfondiimines to access chiral SVI=N-doped heterocycles in high yields and enantioselectivities.

Enantioselective C(sp³)–H alkylation of easily accessible saturated heterocycles is challenging. Now, a nickel-catalysed enantioselective C(sp³)–H alkylation of saturated nitrogen and oxygen heterocycles with olefins has been developed, offering an efficient strategy for the stereoselective formation of C(sp³)–C(sp³) bonds.

A versatile new synthetic route to piperidine-containing structures combines an enzymatic C–H hydroxylation with decarboxylative or deoxygenative radical coupling reactions.

Aminoalcohols are vital motifs in chemical synthesis; however, traditional synthetic technologies relying on polar disconnections have various limitations. Now, such motifs can be expediently accessed by leveraging a radical-based approach, enabling the stereoselective preparation of an array of valuable building blocks.

Enantioenriched alkyl–alkyl bonds are produced from abundant alkenes in one step via Ni-catalysed asymmetric cross-hydrodimerization. This technique overcomes the reactivity and selectivity challenges associated with coupling between two similar nucleophiles.

The development of enantiospecific sulfone reactions has been hindered by the inherent acidity of sulfones, which result in deleterious racemization. Now, the synthesis of enantioenriched diarylalkanes has been reported via sufficiently fast cross-coupling that circumvents racemization of the chiral sulfone.

A strategy for the cobalt-hydride-catalysed enantioselective hydroalkylation of 1,1-disubstituted styrenes is demonstrated, enabling the efficient construction of chiral tertiary carbon centres at the benzyl position. This method overcomes the requirement for a heteroatom-containing substrate, with enantiocontrol instead achieved through C–H···π interactions between the substrate and catalyst.